Preparation and characterization of polyvinylidene fluoride (PVDF) hollow fiber membranes

Polyvinylidene fluoride (PVDF) hollow fiber membranes were prepared by dry/wet and wet phase inversion methods. In spinning these PVDF hollow fibers, dimethylacetamide (DMAc) and polyvinyl pyrrolidone (PVP) were used as a solvent and an additive, respectively. Water was used as the external coagulant. Water or ethanol was used as the internal coagulants. The membranes were characterized in terms of water flux, molecular weight cut-off for the wet membranes. Gas permeation fluxes and effective surface porosity were determined by a gas permeation method for the dried membranes. The cross-sectional structures were examined by scanning electron microscopy. The effects of polymer concentration, air-gap, PVP molecular weight, PVP content in the polymer dope, and the internal coagulant on the permeation properties and membrane structures were examined. Highly permeable PVDF hollow fiber membranes could be prepared from a polymer dope containing low molecular weight PVP and using ethanol as the internal coagulant.     

Effect of solution extrusion rate on morphology and performance of polyvinylidene fluoride hollow fiber membranes using polyvinyl pyrrolidone as an additive

<正>Polyvinylidene fluoride(PVDF) hollow fiber membranes prepared from spinning solutions with different polyvinyl pyrrolidone(PVP) contents(1%and 5%) at different extrusion rates were obtained by wet/dry phase process keeping all other spinning parameters constant.In spinning these PVDF hollow fibers,dimethylacetamide(DMAc) and PVP were used as a solvent and an additive,respectively.Water was used as the inner coagulant.Dimethylformamide(DMF) and water(30/70) were used as the external coagulant.The performances of membranes were characterized in terms of water flux,solute rejection for the wet membranes.The structure and morphology of PVDF hollow fiber were examined by BET adsorption,dry/wet weight method and scanning electron microscopy(SEM).It is found that the increase in PVP content and extrusion rate of spinning solution can result in the increase of water flux and decrease of solute rejection.The improvements of interconnected porous structure and pore size are induced by shear-thinning behavior of spinning solution at high extrusion rates,which could result in the increase of water flux of hollow fiber membranes.The increase of extrusion rate also leads to the increase of membrane thickness due to the recovery effect of elastic property of polymer chains.     

Direct measurement of rheologically induced molecular orientation in gas separation hollow fibre membranes and effects on selectivity

Asymmetric polysulfone hollow fibre membranes for gas separation were spun using a dry/wet spinning process. An optimised four component dope solution was used: 22% (w/w) polysulfone, 31.8% (w/w) N,N-dimethylacetamide, 31.8% (w/ w) tetrahydrofuran and 14.4% (w/w) ethanol. Fibres were spun at low- and high-dope extrusion rates and hence at different levels of shear. Molecular orientation in the active layer of the membranes was measured by plane-polarised infrared spectroscopy. Gas permeation properties (permeability and selectivity) were evaluated using pure carbon dioxide and methane. The spectroscopy indicated that increased molecular orientation occurs in the high-shear membranes. The selectivities of these membranes were heightened and even surpassed the recognised intrinsic selectivity of the membrane polymer. The results suggest that increased shear during spinning increases molecular orientation and, in turn, enhances selectivity.     

Porous poly(vinylidene fluoride) membrane modified with hyperbranched poly(amine‐ester)

Poly(vinylidene fluoride) (PVDF) membranes were hydrophilic modified with hydroxyl group terminated hyperbranched poly(amine‐ester) (HPAE). Fourier transform infrared spectroscopy (FT‐IR) was used to study the chemical change of PVDF membranes. X‐ray photoelectron spectroscopy (XPS) indicated that some HPAE molecules were retained in PVDF membrane through polymer chain coiling. The presence of HPAE would improve the hydrophilicity of PVDF membrane. Scanning electron microscopy (SEM) was employed to characterize the morphology of different membranes. The thermodynamic stability for PVDF/DMAc/HPAE/Water system was characterized by the determination of the gelation values. Precipitation kinetics for PVDF/DMAc/HPAE/Water system was studied by precipitation time measurement. The water contact angle indicated that the hydrophilicity and the biocompatibility corresponding to protein adsorption of PVDF membrane were improved significantly after blending with hydrophilic HPAE molecules. Copyright © 2011 John Wiley & Sons, Ltd.     

Antimicrobial properties of modified and electrospun poly(vinyl phenol)

Antimicrobial polymeric systems were prepared from poly(vinyl phenol) (PVP). Four systems were prepared, two of these based on the modification of the poly(vinyl phenol) by sulfonation with fuming sulfuric acid (SPVP 100k) or by formation of lithium salt of the sulfonated poly(vinyl phenol) brought about by its reaction with lithium hydroxide (LiSPVP 100k). The other two systems were prepared by the electrospinning of poly(vinyl phenol) with molecular weight 20 × 10³ (PVP 20k spun) and 100 × 10³ (PVP 100k spun). The antimicrobial activity of the polymers was examined against different test microorganisms. The plug-cutting technique revealed the potency of SPVP 100k and LiSPVP 100k as antimicrobial agents. SPVP 100k was inhibitory to the growth of gram-negative bacteria (E. coli and Salmonella choleraesius) and gram-positive bacteria (B. subtilis and S. aureus). On the other hand, LiSPVP 100k had antifungal activity against A. niger, T. rubrum and C. albicans. Generally, it was found that polymer morphology and molecular weight affect the activities against test microorganisms. For example, PVP 20k and PVP 100k in their powder form showed no antimicrobial activity. However the results showed that PVP 20k spun has antibacterial activity against B. subtilis, and there is no growth of the tested microorganisms on the electrospun fibers of PVP 100k spun, revealing its property of being a self-sterilizing material (SSM).

Growth inhibition of different concentrations of polymer SPVP. Inoculation: 6 × 10⁴ cells · ml⁻¹, B. subtilis, S. choleraesius, S. aureus and E. coli.     

Effect of coagulant temperature and composition on surface morphology and mass transfer properties of cellulose acetate hollow fiber membranes

Cellulose acetate (CA) hollow fibers were spun via the dry‐jet wet spinning technique under various external coagulant compositions and temperatures. The surface morphology of the resulting hollow fiber was examined using field emission scanning electron microscopy (FESEM) and tapping mode atomic force microscopy (TMAFM). The pure water permeability (PWP) and the retention of dextran of the hollow fiber were also measured. The results showed that both the temperature and composition can affect greatly the surface morphology and hence the permeation performance of hollow fiber membranes when the temperature was over 55°C and the dimethyl formamide (DMF) content was higher than 15%. The on‐line draw ratio increased with the coagulant temperature and DMF content (in the range of 0 to 10%) in the external coagulant. The ultimate tensile strength also increased when the fibers were coagulated in 5–10% DMF and at 70°C. The PWP increased with the DMF content in the coagulant and the coagulant temperature. The retention of dextran decreased with the increase of the DMF content in the coagulant and the coagulant temperature. Copyright © 2005 John Wiley & Sons, Ltd.     

Effect of wet spinning parameters on the properties of novel cellulosic fibres

Novel cellulose fibres (Biocelsol) were spun by traditional wet spinning technique from the alkaline solution prepared by dissolving enzyme treated pulp directly into aqueous sodium zincate (ZnO/NaOH). The spinning dope contained 6 wt.% of cellulose, 7.8 wt.% of sodium hydroxide (NaOH) and 0.84 wt.% of zinc oxide (ZnO). The fibres were spun into 5% and 15% sulphuric acid (H₂SO₄) baths containing 10% sodium sulphate (Na₂SO₄). The highest fibre tenacity obtained was 1.8 cNdtex⁻¹ with elongation of 15% and titre of 1.4 dtex. Average molecular weights and shape of molecular weight distribution curves of the celluloses from the novel wet spun cellulosic fibre and from the commercial viscose fibre were close to each other.     

Structural and performance studies of poly(vinyl chloride) hollow fiber membranes prepared at different air gap lengths

Poly(vinyl chloride) hollow fiber membranes were prepared by the dry/wet and wet/wet spinning technique at different air gap lengths keeping all other spinning parameters constants. Mean pore size, pore size distribution and mean roughness of both the internal and external surfaces of the hollow fibers were determined by atomic force microscopy. Cross-sectional structure was studied by scanning electron microscopy. Ultrafiltration experiments of pure water and aqueous solutions of different solutes having different molecular weights (bovine serum albumin, polyethylene glycol and polyvinyl pyrrolidone) were carried out. It was found that the inner and outer diameters of the PVC fiber membranes decreased with the increase of the air gap distance due to the gravitational force effect. The hollow fiber membranes prepared without and with air gap distances up to 7 cm exhibited a quite symmetric cross-structure consisting of four layers, two small finger-like structure layers at both edges of the hollow fibers and two larger finger-like voids mixed with macrovoids layers in the middle of the cross-section. The outer-middle layer thickness decreased when the air gap distance was increased to 10 cm and disappeared from the cross-section of the hollow membranes prepared with higher air gap lengths than 15 cm. For all dry/wet spun PVC hollow fibers, the outer pore size and the pure water permeation flux both increased with the increase of the air gap distance. In contrast, the solute separation factor decreased with the air gap distance. This was related to the pore size of the external surface of the PVC hollow fibers.     

Characterization and evaluation of commercial poly (vinylidene fluoride)‐g‐sulfonatedPolystyrene as proton exchange membrane

The possibility of developing low‐cost commercial grafted and sulfonated Poly(vinylidene fluoride) (PVDF‐g‐PSSA) membranes as proton exchange membranes for fuel cell applications have been investigated. PVDF‐g‐PSSA membranes were systematically prepared and examined with the focus of understanding how the polymer microstructure (degree of grafting and sulfonation, ion‐exchange capacity, etc) affects their methanol permeability, water uptake, and proton conductivity. Fourier transform infrared spectroscopy was used to characterize the changes of the membrane's microstructure after grafting and sulfonation. The results showed that the PVDF‐g‐PSSA membranes exhibited good thermal stability and lower methanol permeability. The proton conductivity of PVDF‐g‐PSSA membranes was also measured by the electrochemical impedance spectroscopy method. It was found that the proton conductivity of PVDF‐g‐PSSA membranes depends on the degree of sulfonation. All the sulfonated membranes show high proton conductivity at 92°C, in the range of 27 to 235 mScm⁻¹, which is much higher than that of Nafion212 (102 mScm⁻¹ at 80°C). The results indicated that the PVDF‐g‐PSSA membranes are particularly promising membranes to be used as polymer electrolyte membranes due to their excellent stability, low methanol permeability, and high proton conductivity.     

Miscibility and crystallization behavior in blends of poly(methyl methacrylate) and poly(vinylidene fluoride): Effect of star‐like topology of poly(methyl methacrylate) chain

A tetraarmed star‐shaped poly(methyl methacrylate) (s‐PMMA) was synthesized via atom transfer radical polymerization with 2‐bromoisobutyryl pentaerythritol as the initiator. For comparison, a linear PMMA with the identical molecular weight (l‐PMMA) was also prepared. The blends of the two PMMA samples with poly (vinylidene fluoride) (PVDF) were prepared to investigate the effect of macromolecular topological structure on miscibility and crystallization behavior of the binary blends. The behavior of single and composition‐dependent glass transition temperatures was found for the blends of s‐PMMA with PVDF, indicating that the s‐PMMA is miscible with PVDF in the amorphous state just like l‐PMMA. The miscibility was further evidenced by the depression of equilibrium melting points. It is found that the blends of s‐PMMA and PVDF displayed the larger k value of Gordon–Taylor equation than the blends of l‐PMMA and PVDF blends. According to the depression of equilibrium melting points, the intermolecular parameters for the two blends were estimated. It is noted that the s‐PMMA/PVDF blends displayed the lower interaction parameter than l‐PMMA/PVDF blends. The isothermal crystallization kinetics shows that the crystallization of PVDF in the blends containing s‐PMMA is faster than that in the blends containing the linear PMMA. The surface‐folding free energy of PVDF chains in the blends containing s‐PMMA is significantly lower than those in the blends containing l‐PMMA. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2580–2593, 2007     

Effect of the preparation conditions on the formation of asymmetric poly(vinylidene fluoride) hollow fibre membranes with a dense skin

Integrally skinned asymmetric poly(vinylidene fluoride) hollow fibre membranes were prepared and characterized. The effects of phase inversion methods (dry-wet or wet) and spinning conditions, such as the type of solvent (NMP, DMAc), the concentration of polymer in dope solution, temperature of the external coagulation bath and the composition of the inner coagulant on the morphology and on the formation of a dense skin layer were investigated. The structure of the membranes was analyzed by scanning electron microscopy and the gas permeation properties with six different gases (He, H₂, N₂, O₂, CH₄ and CO₂) were measured at 25 °C to confirm the integrity of the selective skin layer. Under the proper conditions highly selective and permeable PVDF hollow fibre membranes were thus obtained by dry-wet spinning of a 30 wt.% PVDF solution in DMAc, using hot water (50 °C) as the external coagulant and a bore fluid of pure water as the internal coagulant. The best membrane had a selective outer skin with an effective thickness of approximately 0.2 μm. The ideal selectivity of the hollow fibres approached or even exceeded the intrinsic ideal selectivity of a dense PVDF film, for instance the selectivity for He over N₂ was 86.2 for the hollow fibre, whereas it was 83.5 for a dense PVDF reference film. DSC and FT-IR/ATR analysis indicated a higher fraction of the β-crystal phase in the selective skin and a high overall crystallinity than in the melt-processed film. The latter explains the relatively high selectivity and low permeability of the membranes. Intrinsic polymer properties make the membranes also suitable for vapour transport than for gas separation.     

Chitin/cellulose blend fibers prepared by wet and dry‐wet spinning

We describe the wet and dry‐wet spinning of multifilament cellulosic composite fibers, namely chitin/cellulose fibers. The direct solution process for the two biopolymers based on an ionic liquid as solvent represents an environmentally friendly and alternative technology to the industrially applied viscose and lyocell process. Both cellulose and chitin possess good solubility in 1‐ethyl‐3‐methylimidazolium propionate ([C₂C₁Im][OPr]) and were spun into multifilament composite fibers. Moreover, for the first time, pure chitin multifilament fibers were obtained by dry‐wet spinning. The effect of chitin addition on the filament properties was investigated and evaluated by microscopic, spectroscopic, and mechanical analyses.     

Polymer electrolyte membranes by in situ polymerization of poly(ethylene carbonate‐co‐ethylene oxide) macromonomers in blends with poly(vinylidene fluoride‐co‐hexafluoropropylene)

Salt‐containing membranes based on polymethacrylates having poly(ethylene carbonate‐co‐ethylene oxide) side chains, as well as their blends with poly(vinylidene fluoride‐co‐hexafluoropropylene) (PVDF‐HFP), have been studied. Self‐supportive ion conductive membranes were prepared by casting films of methacrylate functional poly(ethylene carbonate‐co‐ethylene oxide) macromonomers containing lithium bis(trifluorosulfonyl)imide (LiTFSI) salt, followed by irradiation with UV‐light to polymerize the methacrylate units in situ. Homogenous electrolyte membranes based on the polymerized macromonomers showed a conductivity of 6.3 × 10^?6 S cm^?1 at 20 °C. The preparation of polymer blends, by the addition of PVDF‐HFP to the electrolytes, was found to greatly improve the mechanical properties. However, the addition led to an increase of the glass transition temperature (T_g) of the ion conductive phase by ～5 °C. The conductivity of the blend membranes was thus lower in relation to the corresponding homogeneous polymer electrolytes, and 2.5 × 10^?6 S cm^?1 was recorded for a membrane containing 10 wt % PVDF‐HFP at 20 °C. Increasing the salt concentration in the blend membranes was found to increase the T_g of the ion conductive component and decrease the propensity for the crystallization of the PVDF‐HFP component. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 79–90, 2007     

Molecular modeling simulation and experimental measurements to characterize chitosan and poly(vinyl pyrrolidone) blend interactions

Blends of chitosan and poly(vinyl pyrrolidone) (PVP) have a high potential for use in various biomedical applications and in advanced drug‐delivery systems. Recently, the physical and chemical properties of these blends have been extensively characterized. However, the molecular interaction between these two polymers is not fully understood. In this study, the intermolecular interaction between chitosan and PVP was experimentally investigated using ¹³C cross‐polarization magic angle‐spinning nuclear magnetic resonance (¹³C CP/MAS NMR) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). According to these experimental results, the interaction between the polymers takes place through the carbonyl group of PVP and either the OH? C₆, OH? C₃, or NH? C₂ of chitosan. In an attempt to identify the interacting groups of these polymers, molecular modeling simulation was performed. Molecular simulation was able to clarify that the hydrogen atom of OH? C₆ of chitosan was the most favorable site to form hydrogen bonding with the oxygen atom of C?O of PVP, followed by that of OH? C₃, whereas that of NH? C₂ was the weakest proton donor group. The nitrogen atom of PVP was not involved in the intermolecular interaction between these polymers. Furthermore, the interactions between these polymers are higher when PVP concentrations are lower, and interactions decrease with increasing amounts of PVP. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1258–1264, 2008     

Aromatic polyamides. IV. A novel synthesis of sulfonated poly(para-phenyleneterephthalamide): Polymerization of terephthalic acid and para-phenylenediamine in sulfur trioxide

A novel polyamide condensation reaction of aromatic diamines (usually as strong inorganic acid salts) and aromatic diacids in SO₃ has been discovered. para-Phenylenediamine was polymerized with terephthalic acid in SO₃ at 20–47% polymer concentration to form highly anisotropic (liquid crystalline) sulfonated poly(p-phenyleneterephthalamide) (SPT) solutions (dopes) with inherent viscosities as high as 1.6. Sulfonation of the aromatic diamine ring was a major side reaction. The effects of reaction variables such as temperature, time, monomer concentration, stoichiometry, and solvent acidity on molecular weight were studied. The dopes were spun to fiber, but tensile properties were limited by coagulation problems associated with hydrophilicity of the highly sulfonated polymer. Thermogravimetric analysis of SPT at 20°C/min showed weight loss only above 450°C.     

Melt spinning of propylene carbonate‐plasticized poly(acrylonitrile)‐co‐poly(methyl acrylate)

The primary use of poly(acrylonitrile) (PAN) fibers, commonly referred to as acrylic fibers, is in textile applications like clothing, furniture, carpets, and awnings. All commercially available PAN fibers are processed by solution spinning; however, alternative, more cost‐effective processes like melt spinning are still highly desired. Here, the melt spinning of PAN‐co‐poly(methyl acrylate) (PMA) plasticized with propylene carbonate (PC) at 175°C is reported. The use of methyl acrylate (MA) as comonomer and PC as an external plasticizer renders the approach a combination of internal and external plasticization. Various mixtures of PAN and PC used in this work were examined by rheology, subjected to melt spinning, followed by discontinuous and continuous washing, respectively. The best fibers were derived from a PAN‐co‐PMA copolymer containing 8.1 mol‐% of MA having a number‐average molecular weight M _n of 34 000 g/mol, spun in the presence of 22.5 wt.‐% of PC. The resulting fibers were analyzed by scanning electron microscopy and wide‐angle X‐ray scattering (WAXS), and were subjected to mechanical testing.     

Synthesis and gas permeation properties of poly(vinyl chloride)‐graft‐poly(vinyl pyrrolidone) membranes

A series of amphiphilic graft copolymers consisting of poly(vinyl chloride) (PVC) main chains and poly(vinyl pyrrolidone) (PVP) side chains, i.e. PVC‐g‐PVP, was synthesized via atom transfer radical polymerization (ATRP), as confirmed by ¹H NMR, FT‐IR spectroscopy, and gel permeation chromatography (GPC). Transmission electron microscope (TEM) and small angle X‐ray scattering (SAXS) analysis revealed the microphase‐separated structure of PVC‐g‐PVP and the domain spacing increased from 21.4 to 23.9 nm with increasing grafting degree. All the membranes exhibited completely amorphous structure and high Young's modulus and tensile strength, as revealed by wide angle X‐ray scattering (WAXS) and universal testing machine (UTM). Permeation experimental results using a CO₂/N₂ (50/50) mixture indicated that as an amount of PVP in a copolymer increased, CO₂ permeability increased without the sacrifice of selectivity. For example, the CO₂ permeability of PVC‐g‐PVP with 36 wt% of PVP at 35°C was about four times higher than that of the pristine PVC membrane. This improvement resulted from the increase of diffusivity due to the disruption of chain packing in PVC by the grafting of PVP, as confirmed by WAXS analysis. Copyright © 2011 John Wiley & Sons, Ltd.     

A Preliminary Study on Preparation of the Aromatic/Aliphatic Co‐polyurea as Spun Fibers

Aromatic‐aliphatic co‐polyurea has been synthesized from 4,4 prime‐diphenylmethane diisocyanate (MDI), m‐phenylene diamine (m‐PDA), and 1,6‐diaminohexane (HDA) in DMAc by solution polymerization. The chemical structure of the co‐polyurea has been characterized by ¹H‐NMR. The thermal properties of the copolymers were measured by DSC and TGA. The co‐polyurea solutions were spun into fibers by means of wet spinning. The effects of coagulation conditions on the morphologies and mechanical properties of the co‐polyurea as spun fibers are discussed.     

The role of additives on dope rheology and membrane formation of defect-free Torlon hollow fibers for gas separation

The high demands on high performance membranes for energy, water and life science usages provide the impetus for membrane scientists to search for a comprehensive understanding of membrane formation from molecular level to design membranes with desirable configuration and separation performance. This pioneering work is to elaborate the importance of polymer rheology on hollow fiber formation and reveal the integrated science bridging polymer fundamentals such as polymer cluster size, shear and elongational viscosities, molecular orientation, stress relaxation to membrane microstructure and separation performance for gas separation. Torlon^® poly(amide imide) was employed in this study with various solvent/nonsolvent additives. The effects of additives on polymeric cluster size, hydrogen bonding and dope rheology during the phase inversion have been examined. It is found that hydrogen bonding and strain-hardening characteristics play very important roles in dope rheology and membrane separation performance. Torlon^® possesses strong hydrogen bonds with NMP/water mixtures, the addition of a small amount of water enlarges polymer cluster size, strengthen molecular network (i.e., strain hardening) and facilitate macrovoid-free morphology. However, strong hydrogen bonding may retard chain unfolding during spinning, induce faster relaxation for highly oriented dense-selective skin, and thus reduce gas-pair selectivity. By adjusting dope chemistry and spinning conditions with balanced solubility parameters and dope rheology, we have developed defect-free Torlon^® hollow fiber membranes with an O₂/N₂ selectivity of 8.55 and an ultra-thin layer of 488 Å simply using water as the additive. Fibers spun from dopes containing other additives have the optimal O₂/N₂ selectivity varying from 7.69 to 9.97 at 25 ± 2 °C, and the dense layer thickness varying from 500 Å to 2000 Å. Their corresponding mixed-gas O₂/N₂ selectivity for compressed air varies from 7.12 to 9.00.     

Synthesis of poly(vinylidene fluoride)‐b‐poly(styrene sulfonate) block copolymers by controlled radical polymerizations

Block copolymers based on poly(vinylidene fluoride), PVDF, and a series of poly(aromatic sulfonate) sequences were synthesized from controlled radical polymerizations (CRPs). According to the aromatic monomers, appropriate techniques of CRP were chosen: either iodine transfer polymerization (ITP) or atom transfer radical polymerization (ATRP) from PVDF‐I macromolecular chain transfer agents (CTAs) or PVDF‐CCl₃ macroinitiator, respectively. These precursors were produced either by ITP of VDF with C₆F₁₃I or by radical telomerization of VDF with chloroform, respectively. Poly(vinylidene fluoride)‐b‐poly(sodium styrene sulfonate), PVDF‐b‐PSSS, block copolymers were produced from both techniques via a direct polymerization of sodium styrene sulfonate (SSS) monomer or an indirect way with the use of styrene sulfonate ethyl ester (SSE) as a protected monomer. Although the reaction led to block copolymers, the kinetics of ITP of SSS showed that PVDF‐I macromolecular CTAs were not totally efficient because a limitation of the CTA consumption (56%) was observed. This was probably explained by both the low activity of the CTA (that contained inefficient PVDF‐CF₂CH₂? I) and a fast propagation rate of the monomer. That behavior was also noted in the ITP of SSE. On the other hand, ATRP of SSS initiated by PVDF‐CCl₃ was more controlled up to 50% of conversion leading to PVDF‐b‐PSSS block copolymer with an average number molar mass of 6000 g·mol^?1. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011