Forward osmosis works on a deceptively simple principle. Water spontaneously flows from a feed solution of lower osmotic pressure toward a concentrated draw solution on the other side of a semipermeable membrane. Because the process requires no external pumping pressure, it fouls less than pressure-driven reverse osmosis and can be paired with draw solutes that are easily recovered, or run as a pretreatment stage ahead of reverse osmosis. The heart of any such system is the membrane itself, typically a thin polyamide active layer formed on a porous support. The polyamide layer is created by interfacial polymerization, in which an aqueous amine monomer, usually m-phenylenediamine, meets an organic acyl chloride monomer, usually trimesoyl chloride, at the support’s surface. The reaction is fast and self-limiting, producing an ultrathin but dense film whose thickness, roughness and crosslinking density dictate how fast water moves and how well it rejects solutes.

For years, membrane scientists have tried to tune that film by embedding nanomaterials, a approach known as thin-film nanocomposite design. Nanoparticles of zeolites, metal-organic frameworks, carbon nanotubes, graphene oxide and MXenes have all been slipped into or beneath the polyamide layer, with mixed results. Additives can create extra water pathways and increase hydrophilicity, but they can also introduce defects, agglomerate into clumps that wreck selectivity, or leach out over time. The Iranian team chose a different class of additive altogether: a polyamide-based hyper-crosslinked polymer. Hyper-crosslinked polymers are amorphous, permanently porous networks built from rigid aromatic building blocks locked together by extensive covalent crosslinks. Their high internal surface area, tunable chemistry and chemical stability have made them popular in gas storage and catalysis, and this study puts them to work as a nanofiller for water membranes.

The synthesis itself was characterized with a battery of analytical techniques. Attenuated total reflectance Fourier-transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy confirmed that the hyper-crosslinked polymer had formed successfully, revealing a layered morphology rather than a granular one. Elemental mapping of the material showed that nitrogen-bearing groups were distributed uniformly throughout the structure, a detail that matters because those amide and amine groups interact strongly with water and with the monomers used in membrane fabrication. The high nitrogen content and even dispersion suggested the polymer would integrate well into the polyamide chemistry rather than sitting inertly inside it as a foreign body.

The genuinely clever part of the study is how the polymer gets into the membrane. Rather than blending it into the support or into the aqueous monomer solution, the researchers used what they call an intermediate strategy. The hyper-crosslinked polymer was dispersed in hexane, an organic solvent in which the polymer can be spread as a coating, and that dispersion was applied to the membrane support surface precisely between the aqueous amine phase and the organic acyl chloride phase. The polymer thus occupies the very frontier where interfacial polymerization happens. As the two monomers diffuse toward each other and react, they must contend with a porous, nitrogen-rich, layered material sitting at the reaction zone. The result is a polyamide film whose growth has been sculpted from the inside out.

That sculpting shows up clearly in the membrane’s final properties. The presence of the hyper-crosslinked layer changed the dynamics of monomer diffusion and film nucleation, and the modified active layers came out smoother, thinner and more hydrophilic than films polymerized without the additive. Each of those three attributes pushes performance in the right direction. A thinner film shortens the path water must travel. Greater hydrophilicity improves wetting and reduces the energetic penalty water pays entering the polymer network. Reduced roughness matters for fouling, because contaminants preferentially snag on peaks and valleys, so a smoother surface resists the accumulation of organic matter and dye molecules during long filtration runs. Chemical characterization confirmed the hyper-crosslinked polymer was stably embedded within the polyamide matrix rather than loosely deposited on top of it.

The performance numbers are the study’s headline. An unmodified forward osmosis membrane delivered a water flux of 12.2 liters per square meter per hour, a common benchmark unit abbreviated LMH. At the optimal loading of hyper-crosslinked polymer, flux rose to 23.4 LMH, an increase of more than 90 percent. Pushing the additive loading higher actually backfired, with flux declining again because excess polymer drove the formation of a thicker polyamide layer, which added resistance faster than the extra pathways added permeability. That dose-dependent behavior is typical of nanocomposite membranes and underscores why loading optimization is the central design variable. Importantly, the modified membrane also showed enhanced specific reverse salt flux, meaning that the salt that inevitably leaks backward from the draw solution did so at a rate disproportionately low relative to the water gained, an indicator that selectivity had not been sacrificed for speed.

To test the membrane under realistic and demanding conditions, the team ran a 24-hour continuous process concentrating reactive black B, a widely used anionic dye responsible for much of the colored effluent discharged by the textile industry. The membrane rejected more than 99.9 percent of the dye throughout the run and displayed an anti-fouling tendency, resisting the flux decline that usually plagues dye concentration processes as molecules build up on the membrane surface. The authors attribute this resilience to the combination of smoothness, hydrophilicity and stable integration of the hyper-crosslinked polymer within the active layer. Sustained performance over a full day of operation is a meaningful demonstration that the additive does not wash out, degrade or progressively separate from the polyamide, concerns that have undermined other nanofiller systems.

Why does a porous polymer interlayer boost flux so dramatically? The mechanistic picture, supported by the characterization data, centers on how the intermediate layer reshapes interfacial polymerization itself. Interfacial polymerization is governed by the diffusion of monomers into the reaction zone; anything that moderates that diffusion changes the film’s architecture. The hexane-dispersed hyper-crosslinked coating likely slows the amine monomer’s transport toward the organic phase and provides abundant hydrogen-bonding and amide interaction sites, yielding a film that is simultaneously thinner and more uniformly crosslinked. Related interlayer strategies in the literature, using materials from chitosan and cyclodextrins to covalent organic frameworks and MXene-carbon nanotube assemblies, have shown similar gains, confirming that controlling the reaction frontier is one of the most powerful levers in membrane design. What distinguishes the present work is the use of a permanently porous, polymer-based network rather than an inorganic nanoparticle, which sidesteps problems of particle agglomeration and interfacial incompatibility.

The broader significance lies in what the result says about the permeability-selectivity trade-off, the长久-standing constraint that forces membrane designers to choose between fast and clean. By growing a thinner, smoother, more hydrophilic polyamide film without opening defects, the hyper-crosslinked interlayer improved water transport while preserving rejection of salts and dyes, suggesting the trade-off is not an immutable law but a consequence of how films are made. For desalination, higher flux at equal selectivity translates directly into less membrane area and lower capital cost. For textile wastewater treatment, a membrane that concentrates reactive dyes with near-total rejection and low fouling could enable water reuse and dye recovery in one of the world’s most water-intensive industries. The study, published in Polymer Bulletin with financial and instrumental support from the University of Tehran, adds a versatile new tool, a synthetically tunable porous polymer, to the membrane engineer’s toolkit, and points toward a generation of forward osmosis membranes that no longer ask designers to choose between speed and selectivity.

Subject of Research: Modification of thin-film nanocomposite forward osmosis membranes with a hyper-crosslinked polymer interlayer to enhance water flux, salt rejection and dye concentration

Article Title: Modification of thin film nanocomposite forward osmosis membranes using hyper-crosslinked polymer via intermediate strategy

Article References: Mirsaeidghazi, E., Shakeri, A., & Salehi, H. (2026). Modification of thin film nanocomposite forward osmosis membranes using hyper-crosslinked polymer via intermediate strategy. Polymer Bulletin, 83(12), Article 652. https://doi.org/10.1007/s00289-026-06710-0

Image Credits: AI Generated

DOI: 10.1007/s00289-026-06710-0

Keywords: forward osmosis, thin-film nanocomposite membrane, hyper-crosslinked polymer, interfacial polymerization, polyamide, water desalination, dye concentration, anti-fouling, membrane modification, water flux, reverse salt flux, textile wastewater treatment

The wastewater at the heart of the study came straight from the dyeing process outlet of a textile factory in Isfahan, in central Iran, and it was as dirty as the researchers expected. Chemical oxygen demand, a measure of organic pollution, stood at 8100 milligrams per liter, roughly 135 times the permissible limit for discharge to surface water in Iran. Color intensity registered 23,480 platinum-cobalt units, turbidity 620 nephelometric turbidity units, and total suspended solids 3890 milligrams per liter. Elemental analysis added another layer of concern. The effluent carried 5500 micrograms per liter of aluminum, 5300 of iron, an extraordinary 4200 of the toxic metal thallium, along with antimony, manganese, zinc, copper and lead at levels far above natural background. In Iran only about 20 percent of industrial effluents receive proper treatment before discharge, so the stakes for finding an affordable, effective recipe are high.

Polyaluminum chloride, or PACl, has become a favored coagulant in water treatment because it works across a wide pH range, forms dense and fast-settling flocs and produces less sludge than traditional alum. It is sold in both powdered and liquid form, and the two differ in ways that matter to plant operators. The powdered grade used here contained 28.05 percent aluminum oxide, more than double the 10.48 percent of the liquid grade, but liquid PACl arrives ready to dose, skipping on-site dissolution. The researchers optimized each coagulant independently through standard jar tests on 1-liter samples, defining the optimum as the minimum dose that pushed residual turbidity to 20 NTU or below with the smallest settled sludge volume. Powdered PACl settled on 0.7 grams per liter while liquid PACl required 3.0 milliliters per liter. Every scenario also received sodium hypochlorite at 75 milliliters per liter, chosen because color removal plateaued beyond that dose, and calcium oxide at 1.0 gram per liter, enough to push pH above 10.5 so that dissolved metals could precipitate as hydroxides.

Five treatment configurations were tested in triplicate. The first used powdered PACl, the second liquid PACl, the third a blend of the two, and the fourth and fifth replaced commercial coagulant entirely, or nearly so, with clarifier sludge collected from a local drinking water plant that itself uses PACl. The idea behind the sludge experiments was elegantly circular: the sedimentation basin sludge contains residual polyaluminum chloride and amorphous aluminum hydroxides, so it might act as a free, waste-derived coagulant that simultaneously reduces chemical purchases and diverts waste from landfills. The sludge was mixed into wastewater at a ratio of one part sludge to five parts effluent, the ratio that preliminary trials showed produced maximum floc formation. For the fifth scenario, a modest half-milliliter dose of liquid PACl was added on top of the sludge to test whether virgin and recycled coagulants could work synergistically.

The results split the metals into two camps. Zinc and chromium were the consistent success stories, removed at better than 96 percent in every configuration, with residual zinc concentrations falling below 0.2 micrograms per liter in most scenarios. Thallium, iron, manganese and silicon also dropped by more than 98 percent in the liquid and mixed PACl scenarios. Barium and strontium, by contrast, proved stubbornly recalcitrant, with strontium removal never exceeding 33 percent anywhere in the study, marking these two elements as priority targets for future work. Most striking was the fate of aluminum itself. Clarifier sludge alone removed 99.8 percent of aluminum, the best figure of any scenario, and near-complete removal of lithium and barium besides. But in the fifth scenario, where a small PACl dose was layered onto the sludge, aluminum removal collapsed to zero, and the treated water actually carried more aluminum than the mixed inlet, 4800 micrograms per liter against 4567 going in.

That counterintuitive collapse points to a phenomenon known as overdosing or charge reversal. Coagulants work by neutralizing the negative charges that keep colloidal particles suspended, and beyond the optimum dose the excess positive charge can flip particle surfaces back to a stable, restabilized state, re-suspending material that had already clumped. The sludge, already laden with residual aluminum hydroxides, plus the added PACl apparently tipped the system past that threshold. The authors caution that they did not measure zeta potential, so the mechanism remains a hypothesis, but the practical lessons are unambiguous: more coagulant is not better, combining waste-derived and virgin coagulants without re-optimization can backfire, and fixed-dose recipes are inadequate for wastewater whose composition shifts from batch to batch.

On the conventional pollutants, the combined PACl scenario proved the most robust all-rounder, cutting chemical oxygen demand by 95 percent to a residual 380 milligrams per liter and turbidity by 95 percent, while removing nearly 97 percent of suspended solids. Clarifier sludge alone, despite its dazzling color removal of 99.6 percent, managed only 19.8 percent turbidity removal and 79.9 percent for chemical oxygen demand, confirming that recycled sludge cannot substitute for commercial coagulant on high-strength textile effluent. Electrical conductivity rose in every scenario because calcium oxide and PACl both add dissolved ions, and final pH ranged from 10.74 to 12.51, values that would require neutralization before any discharge or reuse.

The study’s most distinctive move was its scoring system. Rather than ranking treatments by individual removal percentages, the team calculated the grey water footprint, an indicator that translates each pollutant load into the volume of freshwater needed to dilute it to regulatory limits. The critical pollutant for the raw effluent was chemical oxygen demand, driving a footprint of 121,500 cubic meters per month at the facility’s assumed discharge of 750 cubic meters per month, meaning the factory’s pollution load would demand dilution water more than 160 times its own flow. Liquid PACl delivered the best outcome: a 92.96 percent reduction in the footprint, statistically the top performance by analysis of variance, with the combined PACl scenario statistically comparable at 90.85 percent and powdered PACl at 88.27 percent. The sludge-only scenario ranked last at 83.33 percent, despite its standout aluminum and color numbers, because its weak performance on organic matter and turbidity dominated the overall environmental burden.

The grey water footprint also exposed a hidden bottleneck that conventional single-parameter assessment would have missed. In the combined PACl scenario, chemical oxygen demand was cut so effectively that antimony, with only 49 percent removal, quietly became the limiting pollutant, its footprint climbing above the organic load’s. Optimizing one pollutant, in other words, can mask the factor that actually constrains environmental performance. The researchers argue that the metric offers an objective common currency for comparing heterogeneous treatment trains, and note that their chemically enhanced primary treatment approached the footprint reductions typically associated with secondary biological processes such as activated sludge.

For plant operators, the study lands on a concrete protocol: liquid PACl at 3.0 milliliters per liter, sodium hypochlorite at 3750 milligrams per liter of active chlorine, and calcium oxide at 1.0 gram per liter, a combination that cut the grey water footprint by 93 percent while stripping more than 99 percent of thallium and zinc. Clarifier sludge, meanwhile, earns a narrower but genuine role as a free, selective coagulant aid for specific targets such as aluminum and color, and as a landfill-diversion strategy, so long as its dose is optimized independently and its reactive aluminum content is properly characterized. The authors flag open questions, including chlorinated byproducts from hypochlorite oxidation, the economics of full-scale deployment, and the mechanistic differences between PACl formulations, but the headline conclusion stands: when environmental impact is tallied honestly across every pollutant, the liquid form of a familiar coagulant is the strongest tool yet tested for taming textile wastewater.

Subject of Research: Comparative evaluation of PACl coagulant variants and recycled clarifier sludge for treating real textile wastewater using the grey water footprint metric

Article Title: Comparative assessment of PACl variants and clarifier sludge for textile wastewater treatment: A grey water footprint approach

Article References: Tabandeh, L., Arastou, K., & Ebrahimi, A. (2026). Comparative assessment of PACl variants and clarifier sludge for textile wastewater treatment: A grey water footprint approach. Cleaner Engineering and Technology, 34, Article 101319. https://doi.org/10.1016/j.clet.2026.101319

Image Credits: AI Generated

DOI: 10.1016/j.clet.2026.101319

Keywords: textile wastewater, polyaluminum chloride, grey water footprint, coagulation-flocculation, clarifier sludge, heavy metal removal, chemical oxygen demand, sodium hypochlorite, calcium oxide, circular economy, water treatment, industrial effluent