Crystallization Of Chains Research Articles

On the Electrochemical Properties of Poly(Vinylidene Fluoride)/Polythiophene Blends Doped with Lithium‐Based Salt

AbstractIn this study, polymer blends of polythiophene (PTH) and poly(vinylidene fluoride) (PVDF) are investigated by focusing on their structural and electrochemical characteristics. These blends displayed immiscibility confirmed through field emission scanning electron microscopy (FE‐SEM) and interaction assessments. PTH's role as a plasticizer is evident, diminishing crystallinity. A rise in PTH level led to a lower glass transition temperature and a higher melting point, suggesting reduced intermolecular forces and increased polymer chain flexibility. Conversely, a dispersed phase presence elevated the melting point, restricting chain movement and crystallization. The thermal properties of blends are enhanced by increased PTH content. Applying the Vogel–Tammann–Fulcher model to ionic conductivity measurements, it observed a direct relationship between temperature and free volume, impacting conductivity and ion transport numbers. Certain materials exhibit increased activation energies, indicating substantial thermodynamic barriers to local motion. Higher PTH content within the PVDF matrix notably increased the lithium ion transfer number from 0.22 to 0.71, a change tied to the C–S–C structure of polythiophene. However, elevated PTH levels also led to diminished negative charge transfer and ionic conductivity in the PTH‐PVDF blend compared to pure PVDF, likely due to an ionic conduction hindrance.

Concurrently Improving both Mechanical and Electrochemical Performances of Quasi-Solid-State Electrical Double-Layer Capacitors by a Rational Design of Gel Polymer Electrolytes.

Aqueous poly(vinyl alcohol) (PVA) gel electrolyte-based quasi-solid-state electrical double-layer capacitors (QSEDLCs) have been extensively investigated in the past ten years, but challenges remain to fabricate the PVA gel electrolyte possessing both superior mechanical and outstanding electrochemical performances. Herein, we develop a strategy to address this issue by a rational design of PVA gel electrolytes, based on a combination of the freeze-thaw (FT) method and sodium perchlorate (NaClO4)-based water-in-salt (WIS) electrolyte. Our study demonstrates that either the FT method or the NaClO4-based WIS electrolyte can improve both the mechanical performance of the PVA gel electrolyte by increasing the crystallization of PVA chains and the electrochemical performance of the PVA gel electrolyte-based QSEDLC by different mechanisms. In comparison with the conventional solvent evaporation method, this work provides an effective strategy to concurrently improve both the mechanical and electrochemical performances of aqueous QSEDLCs.

Development and characterization of polylactic acid/starch biocomposites – From melt blending to preliminary life cycle assessment

This study presents a comprehensive analysis encompassing melt blending, characterization, life cycle assessment (LCA), and 3D printing of a range of polylactic acid (PLA)/starch biocomposites, with starch content varying from 0 to 50 wt%. To enhance compatibility between the starch particles and the PLA matrix, we utilized a solvent-free method to graft N-octadecyl isocyanate (ODI) molecules onto the surface of the starch particles, resulting in ODI-g-starch, which yielded several improved properties. Notably, toughness and elongation at break improved by approximately 170 % and 300 %, respectively. Moreover, the crystallinity increased from 11.6 % in plain PLA to 30.1 %, suggesting that the uniform dispersion of ODI-g-starch particles acted as nucleating sites for the crystallization of PLA chains. Additionally, viscosity decreased significantly with the introduction of ODI-g-starch particles, indicating their plasticizing effect, thereby enhancing the processability and ease of fabrication of the biocomposite. Crucially, our LCA analysis revealed a significant reduction in the carbon footprint of these biocomposites, up to 18 % and 63 %, compared to plain PLA and selected fossil-based plastics, respectively, upon the incorporation of ODI-g-starch. In summary, our research introduces the newly developed PLA/starch biocomposites as a sustainable and eco-friendly alternative to commercially available plain PLA and specific fossil-based plastics.

(Non)linear Interfacial Rheology of Tween, Brij and Span Stabilized Oil-Water Interfaces: Impact of the Molecular Structure of the Surfactant on the Interfacial Layer Stability.

During emulsification and further processing (e.g., pasteurizing), the oil-water interface is mechanically and thermally stressed, which can lead to oil droplet aggregation and coalescence, depending on the interfacial properties. Currently, there is a lack of insights into the impact of the molecular structure (headgroup and FA chain) of low molecular weight emulsifiers (LME) on the resulting interfacial properties. Additionally, the crystallization/melting of the oil/the emulsifier is often neglected within interfacial rheological experiments. Within this study, the stability of interfaces formed by Tween, Span or Brij was determined as a function of their molecular structure, taking crystallization effects of the LME into account. The headgroup was kept constant while varying the FA, or vice versa. The interfacial film properties (viscoelasticity) were investigated at different temperatures using dilatational and interfacial shear rheology. Both the headgroup and the FA chain impacted the interfacial properties. For the same FA composition, a rather small hydrophobic headgroup resulted in a higher packed interface. The interfacial elasticity increased with increased FA chain length (C12 to C18). This seemed to be particularly the case when the emulsifier crystallized on the interface among cooling. In the case of a densely packed interface, network formation due to chain crystallization of the LME's FA chains occurs during the cooling step. The resulting interface shows predominantly elastic behavior.

Study on the charge transport behaviour of mxene- polymer nanocomposite-based self-assembled floating films at the air-liquid interface

This study explores the fabrication and charge transport behavior of MXene-polymer nanocomposite-based self-assembled floating films at the air-liquid interface. Utilizing ultrasonic dispersion of MXene nanosheets was integrated into a DPP-TTT polymer matrix, significantly enhancing the alignment and crystallization of the polymer chains. The films were fabricated using a unidirectional floating film transfer method (UFTM), which proved to be both simple and cost-effective. UV–visible and grazing incidence X-ray diffraction (GIXD) analyses confirmed increased π–π stacking and improved structural arrangement within the nanocomposites. Organic field-effect transistors (OFETs) fabricated from these films demonstrated that a 3% MXene inclusion resulted in the highest mobility, measuring 3.1 cm2V-1s-1 with an on-off ratio in the order of 104, compared to 1.3 cm2V-1s-1 in pristine DPP-TTT films. However, further increases in MXene content reduced mobility, emphasizing the importance of precise compositional tuning.

Injection molded lightweight composites from tea-stem fiber and polypropylene: Effect of fiber loading on forming properties and cell structure

China boasts abundant tea resources and substantial production output. To facilitate the high-value utilization of by-products generated during tea production, such as tea stems, thereby reducing resource wastage, this study pioneered the preparation of tea-stem fiber-reinforced polypropylene (TF/PP) composites through microcellular injection and conventional molding processes. The effects of tea-stem fiber (TF) content on the formability of foamed and unfoamed composites were compared and analyzed. The findings reveal that the inclusion of TFs fostered the crystallization of polymer chains, decreased the flowability of the composites in their molten state, and enhanced the density, surface hydrophilicity, and thermal stability of the molded composites. In the unfoamed state, composites with 20 wt%, 40 wt%, and 30 wt% TF content exhibited optimal tensile (35.92 MPa), flexural (58.43 MPa), and impact (6.49 KJ/m2) strength, respectively. Upon foaming, composites with TF contents of 30 wt%, 40 wt%, and 30 wt% demonstrated superior tensile (32.84 MPa), flexural (51.31 MPa), and impact (6.94 KJ/m2) strength, respectively. A 30 % TF content in foamed composites yielded the best reinforcement effect, creating an ideal balance of internal interactions. This resulted in mechanical properties that were close to or even exceeded those of unfoamed PP while reducing the density by nearly 6 %. The results from this study contribute towards the high-value application of tea by-products, promoting the development of the global tea economy.

A snapshot review of the crystallization of polymer chains complexed by small molecules focusing on poly(4-vinylpyridine) systems: Opportunities and challenges

A snapshot review of the crystallization of polymer chains complexed by small molecules focusing on poly(4-vinylpyridine) systems: Opportunities and challenges

Crystallization-Induced Self-Assembly of Poly(ethylene glycol) Side Chains in Dithiol-yne-Based Comb Polymers: Side Chain Spacing and Molecular Weight Effects.

The chain architecture and topology of macromolecules impact their physical properties and final performance, including their crystallization process. In this work, comb polymers constituted by poly(ethylene glycol), PEG, side chains, and a dithiol-yne-based ring polymer backbone have been studied, focusing on the micro- and nanostructures of the system, thermal behavior, and crystallization kinetics. The designed comb system allows us to investigate the role of a ring backbone, the impact of varying the distance between two neighboring side chains, and the effect of the molecular weight of the side chain. The results reflect that the governing factor in the crystalline properties is the molar mass of the side chains and that the tethering of PEG chains to the ring backbone brings important constraints to the crystallization process, reducing the crystallinity degree and slowing down the crystallization kinetics in comparison to analogue PEG homopolymers. We demonstrate that the effect of spatial hindrance in the comb-like PEG polymers drives the morphology toward highly ordered, self-assembled, semicrystalline superstructures with either extended interdigitated chain crystals or novel (for comb polymers) interdigitated folded chain lamellar crystals. These structures depend on PEG molecular weight, the distance between neighboring tethered PEG chains, and the crystallization conditions (nonisothermal versus isothermal). This work sheds light on the role of chain architecture and topology in the structure of comb-like semicrystalline polymers.

Microstructural and Hydrophilic Properties of Polylactide Polymer Samples with Various 3D Printing Patterns.

The aim of the work is to study the effect of the 3D printing process on the microstructural and hydrophilic properties of polylactic acid (PLA) samples with various model printing patterns obtained from the black filament PLA by sequentially applying polymer layers using the FDM (fused deposition modeling) method. X-ray phase analysis revealed the partial crystallization of PLA polymer chains in the printed samples, which occurs under thermal and mechanical action on the original amorphous PLA filament during 3D printing to varying degrees, depending on the geometry of the pattern and the morphology of its surface. At the same time, IR spectroscopy data indicate the preservation of all intrastructural chemical bonds of polylactide. Measured at the original installation, the values of the wetting edge angles on the surface of the printed samples are in the range φ = 50-60°, which is significantly less than the right angle. This indicates the hydrophilic properties of the whole sample's surface. At the same time, the influence of different geometries of model drawings in printed samples was found not only on the morphology of the sample's surface according to SEM data but also on its wettability.

Corroborative studies on chain packing characteristics of biological medium-chain-length poly-3-hydroxyalkanoates with different monomeric composition

Medium-chain-length poly-3-hydroxyalkanoates (mcl-PHAs) with varied monomeric compositions were biosynthesized by producer bacteria fed with different fatty acids as carbon source. Octanoic-, lauric-, stearic-, and oleic acids were used to produce four types of mcl-PHAs viz. PHA-OC, PHA-LA, PHA-ST, and PHA-OL, respectively. The mcl-PHAs as film-casted preparations exhibit distinct traits e.g., PHA-OC and PHA-ST films are less flexible than PHA-LA while PHA-OL is a sticky, glue-like material; PHA-ST is opaque whereas PHA-OC, PHA-LA, and PHA-OL displayed transparent layers. The observation is attributed to polymer chain packing and side chain crystallization. A structure-property investigation of these biopolymers was carried out employing different spectroscopic and microscopic analyses in addition to thermal analyses. Comparative analyses of the results were applied in the interpretation and discussion of structure-property relationship.

“Like binding a book”: Interfacial improvement of pre-melted ultrahigh molecular weight polyethylene by pulse vibration molding

Ultrahigh molecular weight polyethylene (UHMWPE) is widely used in industrial, military, and civilian applications owing to its excellent properties. However, the high entanglement degree of UHMWPE melt leads to great difficulties in diffusion and crystallization, which causes poor interfacial strength and mechanical properties of pre-melted UHMWPE, restricting its high-quality processing and high-value recycling. To this end, we propose a rapid interface stitching technology with a pulsed vibration force driving free volume homogenization and chain segment orientation. For the first time, pulse vibration molding (PVM) is applied for the hot-pressing of pre-melted UHMWPE, successfully realizing the interface stitching and product strengthening. Compared with those of the convention molding (CM) samples at 180 °C, the interfacial adhesive fracture toughness of the adhesive samples processed using PVM is increased by 105.9 % and the work of tension of the recycled samples processed using PVM is also increased by 49.09 %, respectively. The fracture strength of the PVM recycled samples at 180 °C reaches 91.77 % of that of the pure samples and the yield strength is also higher, which significantly enhances the recycling of UHMWPE. The characterization results of the interfacial molecular chain entanglement and crystallization show that PVM strengthens the molecular chain diffusion and induces crystallization by promoting the orientation of chain segments, especially at the interface. Consequently, we believe that the proposed technology can play a significant role in the UHMWPE processing methods that involve surface healing.

Composites of Poly(3-hydroxybutyrate) and Mesoporous SBA-15 Silica: Crystalline Characteristics, Confinement and Final Properties.

Several composites based on poly(3-hydroxybutyrate) (PHB) and mesoporous SBA-15 silica were prepared by solvent-casting followed by a further stage of compression molding. The thermal stability, phase transitions and crystalline details of these composites were studied, paying special attention to the confinement of the PHB polymeric chains into the mesopores of the silica. For that, differential scanning calorimetry (DSC) and real-time variable-temperature X-ray scattering at small angles (SAXS) were performed. Confinement was stated first by the existence of a small endotherm at temperatures around 20 °C below the main melting or crystallization peak, being later confirmed by a notable discontinuity in the intensity of the main (100) diffraction from the mesoporous silica observed through SAXS experiments, which is related to the change in the scattering contrast before and after the crystallization or melting of the polymer chains. Furthermore, the usual α modification of PHB was developed in all samples. Finally, a preliminary investigation of mechanical and relaxation parameters was carried out through dynamic-mechanical thermal analysis (DMTA). The results show, in the temperature interval analyzed, two relaxations, named α and β (the latest related to the glass transition) in order of decreasing temperatures, in all specimens. The role of silica as a filler is mainly observed at temperatures higher than the glass transition. In such cases, stiffness is dependent on SBA-15 content.

Toughening mechanism of α/β core-shell structure for high toughness polypropylene random copolymer

Weak interfaces can impede crack propagation in rigid natural materials containing small amounts of organic compounds. Inspired from this, we start from the core-shell structured isotactic propylene (iPP)/polypropylene random copolymers (PPR) homocomposites and construct serval kinds of interfaces to study the toughening mechanisms by applying the crystallization epitaxies of PPR on iPP. Through molecular chain diffusion and crystallization epitaxy, derived models from microscopic core-shell structured crystals in the homocomposites to macroscopic layer-by-layer assemblies with different interfaces are established to magnify the role that each layer plays during crack initiation and propagation. As a result, the ductile β-PP interface can decrease crack tip strength so that a further step of crack initiation is triggered in the composite laminates with a fold of fracture energy consumption compared to the laminates with weak or rigid interfaces. At last, we come back to the core-shell structured homocomposites and toughen them with an improve in impact toughness from ∼10.8 to ∼18.2 kJ/m2 by manipulating the content of ductile interfaces. This work provides a novel research routine and a new toughening mechanism toward the toughening of PP and can be extended to study the fracture mechanisms of other toughening systems with core-shell structures.

Pressure-Driven Piezoelectric Sensors and Energy Harvesting in Biaxially Oriented Polyethylene Terephthalate Film.

This study reports the possibility of using biaxially oriented polyethylene terephthalate (BOPET) plastic packaging to convert mechanical energy into electrical energy. Electricity is generated due to the piezoelectricity of BOPET. Electricity generation depends on the mechanical deformation of the processing aids (inorganic crystals), which were found and identified by SEM and EDAX analyses as SiO2. BOPET, as an electron source, was assembled and tested as an energy conversion and self-powered mechanical stimuli sensor using potential applications in wearable electronics. When a pressure pulse after pendulum impact with a maximum stress of 926 kPa and an impact velocity of 2.1 m/s was applied, a voltage of 60 V was generated with short-circuit current and charge densities of 15 μAcm-2 and 138 nCm-2, respectively. Due to the orientation and stress-induced crystallization of polymer chains, BOPET films acquire very good mechanical properties, which are not lost during their primary usage as packaging materials and are beneficial for the durability of the sensors. The signals detected using BOPET sensors derived from pendulum impact and sieve analyses were also harvested for up to 80 cycles and up to 40 s with short-circuit voltages of 107 V and 95 V, respectively. In addition to their low price, the advantage of sensors made from BOPET plastic packaging waste lies in their chemical resistance and stability under exposure to oxygen, ultraviolet light, and moisture.

Stretching of porous poly (l-lactide-co-ε-caprolactone) membranes regulates the differentiation of mesenchymal stem cells.

Background: Among a variety of biomaterials supporting cell growth for therapeutic applications, poly (l-lactide-co-ε-caprolactone) (PLCL) has been considered as one of the most attractive scaffolds for tissue engineering owing to its superior mechanical strength, biocompatibility, and processibility. Although extensive studies have been conducted on the relationship between the microstructure of polymeric materials and their mechanical properties, the use of the fine-tuned morphology and mechanical strength of PLCL membranes in stem cell differentiation has not yet been studied. Methods: PLCL membranes were crystallized in a combination of diverse solvent-nonsolvent mixtures, including methanol (MeOH), isopropanol (IPA), chloroform (CF), and distilled water (DW), with different solvent polarities. A PLCL membrane with high mechanical strength induced by limited pore formation was placed in a custom bioreactor mimicking the reproducible physiological microenvironment of the vascular system to promote the differentiation of mesenchymal stem cells (MSCs) into smooth muscle cells (SMCs). Results: We developed a simple, cost-effective method for fabricating porosity-controlled PLCL membranes based on the crystallization of copolymer chains in a combination of solvents and non-solvents. We confirmed that an increase in the ratio of the non-solvent increased the chain aggregation of PLCL by slow evaporation, leading to improved mechanical properties of the PLCL membrane. Furthermore, we demonstrated that the cyclic stretching of PLCL membranes induced MSC differentiation into SMCs within 10days of culture. Conclusion: The combination of solvent and non-solvent casting for PLCL solidification can be used to fabricate mechanically durable polymer membranes for use as mechanosensitive scaffolds for stem cell differentiation.

Bottlebrush Elastomers with Crystallizable Side Chains: Monolayer-like Structure of Backbones Segregated in Intercrystalline Regions.

Bottlebrush (BB) elastomers with water-soluble side chains and tissue-mimetic mechanical properties are promising for biomedical applications like tissue implants and drug depots. This work investigates the microstructure and phase transitions of BB elastomers with crystallizable polyethylene oxide (PEO) side chains by real-time synchrotron X-ray scattering. In the melt, the elastomers exhibit the characteristic BB peak corresponding to the backbone-to-backbone correlation. This peak is a distinct feature of BB systems and is observable in small- or medium-angle X-ray scattering curves. In the systems studied, the position of the BB peak ranges from 3.6 to 4.8 nm in BB elastomers. This variation is associated with the degree of polymerization of the polyethylene oxide (PEO) side chains, which ranges from 19 to 40. Upon crystallization of the side chains, the intensity of the peak decays linearly with crystallinity and eventually vanishes due to BB packing disordering within intercrystalline amorphous gaps. This behavior of the bottlebrush peak differs from an earlier study of BBs with poly(ε-caprolactone) side chains, explained by stronger backbone confinement in the case of PEO, a high-crystallinity polymer. Microstructural models based on 1D SAXS correlation function analysis suggest crystalline lamellae of PEO side chains separated by amorphous gaps of monolayer-like BB backbones.

Revealing the Effect of the Molecular Weight Distribution on the Chain Diffusion and Crystallization Process under a Branched Trimodal Polyethylene System.

With the increasing demand for high-end materials, trimodal polyethylene (PE) has become a research hotspot in recent years due to its superior performance compared with bimodal PE. By means of molecular dynamics (MD) simulations, we aim to expound the effect of the molecular weight distribution (MWD) on the mechanism of nucleation and crystallization of trimodal PE. The crystallization rate is faster when short-chain branching is distributed on a single backbone compared to that on two backbones. In addition, as the content of high molecular weight backbone decreases, the time required for nucleation decreases, but the crystallization rate slows down. This is because low molecular weight backbones undergo intra-chain nucleation and crystallize earlier due to the high diffusion capacity, which leads to entanglement that prevents the movement of medium or high molecular weight backbones. Furthermore, crystallized short backbones hinder the movement and crystallization of other backbones. What is more, a small increase in the high molecular weight branched backbone of trimodal PE can make the crystallinity greater than that of bimodal PE, but when the content of high molecular weight backbone is too high, the crystallinity decreases instead, because the contribution of short and medium backbones to high crystallinity is greater than that of long backbones.

Polyhydroxyurethane and Poly(ethylene oxide) Multiblock Copolymer Networks: Crosslinking with Polysilsesquioxane, Reprocessing and Solid Polyelectrolyte Properties.

This contribution reports the synthesis of polyhydroxyurethane (PHU)-poly(ethylene oxide) (PEO) multiblock copolymer networks crosslinked with polysilsesquioxane (PSSQ). First, the linear PHU-PEO multiblock copolymers were synthesized via the step-growth polymerization of bis(6-membered cyclic carbonate) (B6CC) with α,ω-diamino-terminated PEOs with variable molecular weights. Thereafter, the PHU-PEO copolymers were allowed to react with 3-isocyanatopropyltriethoxysilane (IPTS) to afford the derivatives bearing triethoxysilane moieties, the hydrolysis and condensation of which afforded the PHU-PEO networks crosslinked with PSSQ. It was found that the PHU-PEO networks displayed excellent reprocessing properties in the presence of trifluoromethanesulfonate [Zn(OTf)2]. Compared to the PHU networks crosslinked via the reaction of difunctional cyclic carbonate with multifunctional amines, the organic-inorganic PHU networks displayed the decreased reprocessing temperature. The metathesis of silyl ether bonds is responsible for the improved reprocessing behavior. By adding lithium trifluoromethanesulfonate (LiOTf), the PHU-PEO networks were further transformed into the solid polymer electrolytes. It was found that the crystallization of PEO chains in the crosslinked networks was significantly suppressed. The solid polymer electrolytes had the ionic conductivity as high as 7.64 × 10-5 S × cm-1 at 300 K. More importantly, the solid polymer electrolytes were recyclable; the reprocessing did not affect the ionic conductivity.

Significantly enhanced crystallization of polylactide Ingeo 4032D by polyethylene ionomer

Poly(lactic acid) (PLA) is the most important biopolymer material due to its excellent biocompatibility, biodegradability, and processability. However, its widespread applications were significantly limited by its low crystallization rate. While adding small molecule organic nucleating agents became a commonly used method in enhancing the crystallization rate, these nucleating agents generally suffer from limited solubility, which caused compromised nucleation efficiency and undesirable product appearance due to their precipitation onto the surface of the PLA products overtime. Here we report an efficient method for improving the PLA crystallization performance by using polyethylene (PE) ionomer as an additive in the PLA/TMC300 (an organic nucleating agent) nucleation/crystallization process. The added ionomer led to enhanced crystallization rate and reduced crystalline grain size. The resulting PLA from crystallization with TMC300 and ionomer showed reduced glass transition temperatures, reduced contact angles, and enhanced elastic modulus without compromising the impact strength and elongation at break. A possible mechanism was proposed for the remarkable synergistic effects of ionomer and TMC-300 in modifying the PLA crystallization process with the ionomer playing the roles of both plasticizer (enhanced PLA chain mobility and crystallization rate) and compatibilizer (enhanced dissolution and dispersion of TMC300 in the PLA matrix). This work offered a promising strategy for crystallization and modification of PLA materials.

Synergetic effect of microfluidic flow and ultrasonication on chains pre-ordering in conjugated polymer solution

Multi-physical fields solution processing strategy provides a universal and facile way to prepare various conjugated polymer (CP) films and high-performance devices, whereas the hierarchical structures evolution and crystallization of the polymer chains are elusive particularly under the far-from-equilibrium state in solution. In this work, we employed a combined microfluidic flow and ultrasonication strategy (FU) for CP solution processing and found a pronounced synergetic effect of these fields in promoting the pre-ordering of chains in solution. This conformation order and anisotropy of the solution were revealed by using UV–Vis absorption, polarized optical microscopy (POM) and cryogenic transmission electron microscopy (Cryo-TEM) characterizations. A non-classical nucleation model for the conjugated polymer crystallization in the procedure of non-equilibrium solution processing was confirmed. The roles of microfluidic flow and ultrasonication on the chain aggregation and crystallization were addressed with the aim of a multi-physical simulation based on pressure acoustics streaming, fluid heat transfer and thermoviscous boundary layer impedance. Compared to pristine solutions, the FU strategy showed improved solution anisotropy and crystallization kinetics, substantially giving rise to a larger crystallinity in films and much increased mobilities for the organic field-effect transistor (OFET) devices by more than an order of magnitude. With an appropriate balance between the solvation and interchain interactions, the FU processing strategy is universal for regulation of chains conformation and aggregation in conjugated polymer solution.