The metals in question are among the most frequently detected pollutants in industrial wastewater. Lead and copper ions originate from mining, electroplating, battery manufacturing, and metallurgical processing, and even at trace concentrations they can trigger neurological, renal, and cardiovascular disorders in humans while accumulating in aquatic food chains. Conventional remediation techniques such as chemical precipitation, ion exchange, coagulation–flocculation, and activated carbon adsorption all carry drawbacks, including high operational costs, the generation of contaminated sludge, and poor performance at low metal concentrations. Membrane-based separation has emerged as an appealing alternative because of its operational simplicity, compact footprint, and potential for continuous treatment, but the performance of any membrane depends heavily on how it is made.

That is where the Brazilian team’s choice of fabrication method becomes significant. Most nanofiber membranes described in the literature are produced by electrospinning, a technique that draws fibers from a polymer solution using high voltage. Electrospinning produces excellent fibers but suffers from low production rates and high energy consumption, which have limited its industrial adoption. The researchers instead used solution blow spinning, or SBS, a technique that replaces the electric field with a stream of compressed air. In SBS, the polymer solution is fed through a concentric nozzle while pressurized air simultaneously stretches the emerging jet into fine fibers, which are collected on a rotating drum. The method requires no high-voltage equipment, offers higher throughput, and still yields highly porous micro- and nanofibrous mats, making it an attractive route to membranes that could one day be manufactured at scale.

To give the inherently hydrophobic PVDF an affinity for metal ions, the team dispersed montmorillonite clay into the polymer solution at loadings ranging from 3 to 30 percent by weight relative to the polymer. Montmorillonite is a layered silicate with a high specific surface area and a substantial cation exchange capacity. Its negatively charged interlayer spaces and surface hydroxyl groups attract divalent metal cations such as Pb²⁺ and Cu²⁺ through electrostatic interactions and ion exchange, effectively turning the clay particles scattered through the fibrous network into a dense population of active adsorption sites. The researchers fabricated two families of membranes: pristine PVDF nanofiber mats and PVDF–clay composites, keeping the solution volume constant at five milliliters for every production run so that thickness differences could be attributed to the clay content itself.

Scanning electron microscopy confirmed that the process worked as intended. The membranes displayed uniform, smooth, cylindrical fibers with only occasional bead-like imperfections, a sign that the spinning parameters—30 percent polymer concentration, a solution flow rate of 76 microliters per hour, air pressure of 140 kilopascals, a working distance of 21 centimeters, and a collector speed of 80 revolutions per minute—were well chosen. X-ray diffraction revealed the characteristic crystalline phases of PVDF alongside clay-derived peaks corresponding to quartz and aluminum oxide, confirming that the filler was genuinely incorporated into the fibers. At the highest loading of 30 percent, however, clay agglomerates began to appear, producing structural defects, thinner and more fragile films, and, above that threshold, outright clogging and failure of fiber formation.

Before testing adsorption, the team determined the point of zero charge of the membranes, the pH at which the surface carries equal numbers of positive and negative charges. This value came out at 6.9 in pure water and 6.4 in a water–ethanol mixture, and the adsorption experiments were conducted near these values to minimize interference from the liquid medium. Batch tests, in which membrane pieces of roughly 50 milligrams were stirred with 20 milliliters of metal solution at 5 milligrams per liter, showed a familiar pattern: rapid uptake in the first hours as abundant adsorption sites were available, followed by a gradual slowdown as those sites filled. Adsorption was consistently higher in the water–ethanol mixture, which the authors attribute to ethanol acting like a surfactant, lowering the surface tension of water and helping the solution wet the hydrophobic polymer and penetrate the spaces between fibers to reach buried clay sites.

The kinetic and equilibrium analysis told a coherent mechanistic story. A pseudo-first-order model fit the data poorly, with correlation coefficients as low as 0.674, whereas the pseudo-second-order model tracked the experiments closely in both media, indicating that the rate-limiting step involves chemical interaction—chemisorption—between the metal ions and functional sites on the clay surface. Equilibrium data were best described by the Langmuir isotherm, which assumes monolayer adsorption on a finite number of identical sites, and the calculated maximum adsorption capacities matched the experimental values well. The dimensionless separation factor derived from the Langmuir constant was below one in every test, confirming that adsorption of both metals is thermodynamically favorable. Still, the Langmuir constants were low, between 0.044 and 0.298, and more than half of the dissolved metal remained in solution at equilibrium in the static tests—a limitation the researchers trace directly to the hydrophobic PVDF matrix, which impedes ion access to clay sites in stagnant water.

The picture changed dramatically when the membranes were operated as filters. In dead-end filtration experiments, in which the metal solution was forced through a 12.5 square centimeter membrane area under roughly one bar of pressure from a vacuum pump, removal efficiencies soared above 90 percent, with the membrane containing 10 percent clay achieving 92 percent copper removal in aqueous medium. The lead removal performance matched that of comparable electrospun membranes reported in the literature, but with the advantage of a faster, cheaper production process. Even pure PVDF removed a meaningful fraction of the metals, demonstrating that the porous fibrous architecture itself contributes to capture. The combined mechanism—physical retention by the dense fiber network working in tandem with adsorption at clay sites under pressure-driven flow—proved far more effective than batch adsorption alone, because the applied pressure overcomes the wetting resistance that limits ion penetration in static conditions.

Intriguingly, more clay was not always better. At 30 percent loading, filtration performance deteriorated: aggregates identified by energy-dispersive X-ray analysis acted as bypass routes that let water, and the metals it carried, slip through without contacting adsorbent sites, while the weakened mechanical properties of the highly loaded membranes allowed pores to widen under pressure. The study also revealed a classic trade-off between selectivity and permeability, with thicker, less permeable membranes delivering the highest selectivity. The authors are candid about the work’s limits: no regeneration or reuse studies were performed, long-term stability remains untested, and performance in multicomponent, real-world wastewater has yet to be assessed. Future work, they note, should address membrane reuse, metal leaching, permeability–selectivity trade-offs, and continuous-flow operation. Even so, the message is clear: solution blow spinning can rapidly produce PVDF–clay nanofiber membranes that excel as filtration materials, and with moderate clay loadings of around 10 percent, they offer a promising, scalable route to stripping toxic lead and copper from contaminated water.

Subject of Research: PVDF–montmorillonite clay nanofibrous membranes produced by solution blow spinning for the removal of lead and copper ions from contaminated water

Article Title: Removal of Pb and Cu metals by PVDF/clay membranes obtained through solution blow spinning technique

Article References: da Cruz Dias, G., Zadorosny, L., Sanches, A. O., dos Santos, M. C., & Malmonge, L. F. (2026). Removal of Pb and Cu metals by PVDF/clay membranes obtained through solution blow spinning technique. Journal of Materials Science: Polymers, 1(1), Article 18. https://doi.org/10.1007/s44493-026-00020-7

Image Credits: AI Generated

DOI: 10.1007/s44493-026-00020-7

Keywords: solution blow spinning, PVDF, montmorillonite clay, nanofibrous membranes, heavy metal removal, lead, copper, water treatment, adsorption kinetics, Langmuir isotherm, membrane filtration, wastewater remediation

PVDF is a semicrystalline fluoropolymer prized for its chemical resistance, thermal robustness, mechanical durability, and innate hydrophobicity. It is also polymorphic, crystallizing in phases that include the nonpolar alpha form and the piezoelectric beta phase, a combination that makes it attractive for filtration membranes, sensors, energy harvesters, and water-oil separation systems. The Brazilian group, led by Gabriel da Cruz Dias of the Universidade Estadual de Maringá together with colleagues at UNESP and UNIFUNEC, asked a question that most prior studies had avoided: what happens when clay content climbs far beyond the low loadings, typically at or below 10 percent by weight, that researchers usually dare to use?

The answer required an unconventional fabrication route. Electrospinning, the dominant method for producing polymer nanofibers, relies on high electric fields, delivers modest production rates, and is difficult to scale. Solution Blow Spinning instead uses a pressurized gas jet to draw fibers from a polymer solution, offering higher throughput, simpler equipment, and lower cost. In the experiments, PVDF was dissolved in N,N-dimethylformamide at a concentration of 30 percent weight per volume, and montmorillonite K10 clay was dispersed in the solvent beforehand at levels of 3, 5, 10, 20, and 30 percent relative to the polymer mass. The mixture was fed through the nozzle at 76 microliters per minute under an air pressure of 140 kilopascals, with a working distance of 21 centimeters, yielding self-supported fibrous mats whose average fiber diameters stayed below 200 nanometers.

Scanning electron microscopy revealed that pure PVDF fibers were uniform, smooth, and cylindrical, with only occasional bead defects caused by jet instability and incomplete solvent evaporation. As clay content rose, imperfections multiplied. At 30 percent loading, clay clusters became prominent, hanging from the fibers like stones tied to a string and, according to the authors’ vivid analogy, pulling the loaded jets toward the collector faster than the polymer threads could follow. The consequence was measurable: with a constant 5 milliliters of solution for every production run, composite thickness fell only slightly up to 10 percent clay but dropped considerably at 20 and 30 percent, signaling that the process was losing efficiency as aggregates sabotaged fiber deposition.

Perhaps counterintuitively, the viscosity of the spinning solutions decreased as more clay was added. The explanation lies in sample preparation: because the clay was first dispersed in DMF, higher clay concentrations demanded additional solvent, and this dilution effect outweighed the thickening expected from suspended solid particles. Thinner solutions allowed polymer chains to disentangle and stretch more easily under the constant air pressure, producing finer fibers at high clay contents. Up to 10 percent clay, where solvent content remained constant, the trend reversed, with diameters rising slightly as viscosity increased—behavior consistent with earlier electrospinning and blow-spinning studies of clay-laden polymer solutions.

Elemental mapping by energy-dispersive X-ray spectroscopy confirmed that silicon, oxygen, and aluminum from the clay were distributed fairly homogeneously through the fibrous networks, with localized clustering at the two highest loadings. X-ray diffraction showed that both the alpha and beta crystalline phases of PVDF coexisted in every mat and, crucially, that clay addition did not alter this balance. The researchers attribute the phase formation to the blow-spinning process itself, in which rapid solvent evaporation favors the alpha phase while simultaneous fiber stretching promotes the beta phase, and they note that room-temperature processing may explain why clay did not act as the beta-phase nucleation catalyst reported in studies using heated routes. Differential scanning calorimetry reinforced the structural picture, showing a single melting peak near 176 degrees Celsius for all compositions, with a shoulder attributed to melting of the interfacial region between crystalline and amorphous lamellae.

Thermogravimetric analysis, however, delivered a caution. Pure PVDF remained stable to roughly 420 degrees Celsius before losing about 75 percent of its mass through dehydrofluorination, the reaction that releases hydrogen fluoride and leaves behind unsaturated carbon species. The composites degraded in two steps, and an initial degradation peak intensified with clay content, evidence that dispersed rather than exfoliated clay particles, and particularly the metal ions within them, catalyzed chain scission. Without the barrier effect that well-exfoliated clay layers would provide, higher filler contents reduced the composite’s thermal stability rather than enhancing it.

Mechanical testing traced a clear arc from reinforcement to collapse. Pure PVDF membranes were highly ductile, stretching about 58 percent before breaking with an elastic modulus near 13 megapascals, behavior typical of fibrous mats in which fibers align and reorient under load. Adding up to 5 percent clay increased both stiffness and tensile strength, because rigid particles acted as bridging points that transferred stress between neighboring fibers. Beyond roughly 5 to 10 percent, however, performance deteriorated sharply: elongation at break fell steadily with filler content, and at 30 percent clay the tensile strength had dropped by about 54 percent relative to pure PVDF. The culprit, visible in both electron micrographs and elemental maps, was agglomeration—defects that concentrate stress and sever efficient load transfer through the network.

Wettability measurements added an unexpected twist. All composites remained hydrophobic, with static water contact angles of 114 degrees for pure PVDF and, apart from a slight dip at 3 percent clay, rising values of 115, 119, 122, and 123 degrees as clay content climbed to 5, 10, 20, and 30 percent. Because montmorillonite is inherently hydrophilic, the trend runs against intuition, but the authors attribute it to increased surface roughness imparted by clay particles, which amplifies the low surface energy conferred by PVDF’s strongly bonded carbon-fluorine groups. A water-ethanol mixture reduced the contact angles, offering a simple lever for tuning wettability in applications such as filtration and separation without changing the material’s composition.

The study’s broader message is twofold. First, Solution Blow Spinning is a genuinely viable and scalable route to PVDF-based fibrous nanocomposites, producing sub-200-nanometer fibers at productivity levels electrospinning cannot match—here, 5 milliliters of a 30 percent solution yielded mats roughly 500 micrometers thick. Second, the technique’s tolerance for inorganic fillers has hard limits. The 30 percent formulation, with its thin, fragile mats, abundant aggregates, and depressed mechanical performance, marks a boundary that future work should not cross without improved dispersion strategies. For now, the sweet spot sits at low clay contents, where composites combine hydrophobic surfaces, controllable porosity, and enhanced stiffness, positioning them for filtration, environmental remediation, and membrane applications. The authors suggest that next steps should focus on refining filler dispersion, optimizing processing parameters, and evaluating functional metrics such as permeability, selective adsorption, and long-term stability under realistic operating conditions.

Beyond the specific findings, the study offers a useful methodological template for anyone probing the limits of high-throughput fiber fabrication. Rather than presenting a single optimized formulation, the authors deliberately swept a wide compositional range and documented where each characterization technique registered a change in behavior. This threshold-mapping approach—tracking solution viscosity, fiber diameter, mat thickness, crystalline phase content, degradation onset, tensile response, and contact angle as a function of filler loading—makes the results directly comparable across laboratories and provides benchmarks against which future dispersion strategies can be judged.

The work also situates itself within a broader shift in fibrous membrane research. Electrospinning remains the reference technique for producing submicron polymer fibers, but its dependence on high voltages and modest throughput has long constrained industrial adoption. Solution Blow Spinning, by contrast, requires only a pressurized gas supply, a syringe pump, and a rotating collector, all of which are inexpensive and straightforward to operate. The demonstration that this setup can accommodate inorganic loadings up to 30 percent by weight—while still yielding self-supported mats with sub-200-nanometer fibers—suggests that the technique’s real bottleneck is not fiber formation itself but the rheology and homogeneity of the precursor solutions.

For applications, the combination of hydrophobic surfaces, interconnected porosity, and tunable stiffness is particularly relevant to membrane-based separations, where water-repellent fibrous mats are sought for treatments involving oily wastewater or for supporting catalytic and adsorptive phases. The observation that a simple water-ethanol test liquid lowers contact angles hints at how wetting behavior could be tuned in practice, either through liquid choice or through post-processing that modifies surface texture. The authors’ open-access publication, released in the first volume of the Journal of Materials Science: Polymers, makes the full dataset available to groups working on scalable nanocomposite fibers, and the identification of agglomeration as the dominant failure mode above roughly 10 percent clay gives a clear target for subsequent studies employing surface-modified or organophilic clays, alternative solvents, or in-line dispersion methods.

Subject of Research: Fabrication of hydrophobic PVDF/clay fibrous nanocomposites via solution blow spinning with tunable mechanical properties

Article Title: Hydrophobic PVDF/clay fibrous nanocomposites prepared by solution blow spinning with tunable mechanical properties

Article References: Dias, G. D. C., Zadorosny, L., Sanches, A. O., de Paula, F. R., dos Santos, M. C., & Malmonge, L. F. (2026). Hydrophobic PVDF/clay fibrous nanocomposites prepared by solution blow spinning with tunable mechanical properties. Journal of Materials Science: Polymers, 1(1), Article 19. https://doi.org/10.1007/s44493-026-00018-1

Image Credits: AI Generated

DOI: 10.1007/s44493-026-00018-1

Keywords: PVDF, montmorillonite clay, solution blow spinning, nanocomposites, nanofibers, hydrophobicity, contact angle, tensile properties, thermal stability, crystalline phases, fibrous membranes, morphology