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Salt stabilises soap films at 5 nm, preventing rupture

2026-07-08 08:15 UTC pith:KTVHUEG2

load-bearing objection Salt stabilises Newton black films at ~5 nm in dynamic vertical soap films, extending lifetime across all humidities tested the 2 major comments →

arxiv 2607.06363 v1 pith:KTVHUEG2 submitted 2026-07-07 physics.flu-dyn

Stabilising Evaporating Soap Films with Salt

Victor Ziapkoff , Fran\c{c}ois Boulogne , Anniina Salonen , Emmanuelle Rio This is my paper
classification physics.flu-dyn PACS 47.57.Bc68.15.+e82.70.Kj
keywords soap filmNewton black filmelectrolyteevaporationfilm stabilityDLVOsurfactantNaCl
verification ladder T0 review T1 audit T2 compute T3 formal T4 reserved

The pith

A machine-rendered reading of the paper's core claim, the machinery that carries it, and where it could break.

This paper investigates what happens when you add a high concentration of sodium chloride (at seawater-like levels) to vertical soap films made from a surfactant called TTAB, under controlled humidity. The authors find that salt does not measurably change how the film thins during most of its life: drainage and evaporation dynamics are nearly identical with and without salt down to about 100 nm. The decisive effect of salt appears only at the very end. Without salt, films rupture when they reach roughly 10 nm. With salt, films instead stabilise at a thickness of about 5 nm, forming what is called a Newton black film, a structure held together by steric repulsion between surfactant molecules. This 5 nm plateau persists across all humidities tested, and the plateau lifetime increases with humidity. The paper also quantifies evaporation rates using a natural-convection model and tracks how salt concentrates as the film thins, finding that salt's effect on evaporation is negligible down to 100 nm. The central discovery is that the lifetime extension from salt is not due to slower thinning but to the formation of a stable ultrathin film that arrests rupture.

Core claim

The addition of NaCl at 32.5 g/L to TTAB soap films causes a stable Newton black film to form at approximately 5 nm thickness, observable as a thickness plateau that persists across all humidities tested (40 to 100 percent). Without salt, no such plateau forms and films rupture at about 10 nm. Salt has no measurable effect on drainage or evaporation rates down to 100 nm, so the stabilisation is purely a nanoscale structural effect: the transition from electrostatically stabilised common black films to sterically stabilised Newton black films, driven by the known critical electrolyte concentration for this surfactant system.

What carries the argument

The central object is the Newton black film (NBF), a roughly 5 nm thick soap film stabilised by steric repulsion between surfactant head groups at the two air-water interfaces. The paper identifies its formation via interferometric thickness measurements showing a plateau at 5 nm, and connects it to the DLVO framework's distinction between common black films (electrostatically stabilised, tens of nm thick) and NBFs (sterically stabilised, ~5 nm), with the transition governed by a critical electrolyte concentration.

Load-bearing premise

The evaporation model assumes that the drainage rate inside the film does not depend on atmospheric humidity, which allows the authors to subtract the saturated-atmosphere curve to isolate evaporation. This is physically reasonable but not independently verified for this system. It does not affect the central Newton black film observation, which is a direct thickness measurement, but it does influence the quantitative evaporation rates and salt concentration trajectories the纸

What would settle it

If interferometric measurements at the 5 nm plateau were shown to be artefacts of the single-layer optical model rather than genuine thickness stabilisation, or if the plateau were demonstrated to be a transient kinetic arrest rather than a thermodynamically stable Newton black film, the central claim would be undermined.

Watch this falsifier — get emailed when new claim-graph text bears on it.

Editorial analysis

A structured set of objections, weighed in public.

Desk editor's note, referee report, simulated authors' rebuttal, and a circularity audit.

Referee Report

2 major / 8 minor

Summary. This manuscript investigates the effect of NaCl (32.5 g/L) on the stability, thinning dynamics, and rupture of vertical TTAB soap films under controlled humidity. The central experimental finding is that salt enables the formation of a stable Newton Black Film (NBF) at a thickness plateau of approximately 5 nm, whereas salt-free films rupture at ~10 nm without forming any stable plateau. This NBF plateau is observed across all humidities tested (Rh = 40–100%) and multiple salt concentrations. The authors further develop an evaporation model (§5.2–5.3) that couples drainage with buoyancy-driven convective evaporation and salt-concentration-dependent vapor pressure, showing that salt has negligible effect on thinning dynamics down to 100 nm. Film lifetime statistics (N > 400 per condition) and a return-map analysis of rupture stochasticity (§5.1) are also presented.

Significance. The paper addresses a well-defined and physically relevant problem: how salt influences the stability of dynamically generated foam films, with direct motivation from ocean-atmosphere bubble rupture. The central NBF observation is a direct interferometric measurement, not a model-derived result, which is a significant strength. The authors provide reproducibility checks (10 films per condition), use a three-layer Duyvis model to cross-validate the plateau thickness against neutron scattering data (Simister et al. 1992), and confirm film survival during the plateau via an independent force sensor. The evaporation model uses physically grounded expressions (Eq. 5.7, 5.10) with O(1) fitting prefactors, and the extracted evaporation rates (je = [21, 13, 5] nm/s) are consistent with prior measurements by Champougny et al. (2018). The systematic variation of humidity and salt concentration, combined with the salt-concentration evolution model (Fig. 7b), adds quantitative depth. The finding that no CBF forms in the absence of salt is unexpected and stimulates further investigation.

major comments (2)
  1. §4.1, Fig. 3(b): The central claim of NBF stabilisation at ~5 nm rests on interferometric thickness measurements at the stated lower limit of the method (5 nm, σ = ±1 nm). At h ≈ 5 nm, the round-trip optical path difference is ~10 nm, corresponding to λ/45–λ/80 of the measured wavelength range (450–800 nm), where reflectance spectra become nearly flat and thickness extraction is ill-conditioned. The paper mitigates this with the three-layer Duyvis model (Eq. 4.1) yielding h† ≈ 0.52 nm consistent with neutron scattering, and the force sensor independently confirms film survival during the plateau. However, the concern is not fully resolved: if the spectrometer returns near-constant reflectance below some threshold, the fitting pipeline could produce an apparent plateau at a fixed thickness that is actually a measurement floor. To fully close this issue, the authors should include at least
  2. one representative raw reflectance spectrum from the plateau phase (alongside the fitted model spectrum) in a supplementary figure, demonstrating that meaningful spectral variation is present at h ≈ 5 nm and that the thickness extraction is not degenerate. This is the single most load-bearing point for the central claim and should be addressable within the manuscript scope.
minor comments (8)
  1. §5.2, Eq. (5.5): The assumption that drainage rate jd is independent of atmospheric humidity is physically motivated but unverified for this system. The authors should add a brief discussion of potential coupling mechanisms (e.g., temperature gradients from evaporative cooling affecting viscosity, Marangoni stresses) and an estimate of their magnitude. This does not affect the central NBF observation but does bear on the quantitative evaporation rates je = [21, 13, 5] nm/s.
  2. §4, Fig. 3: The practice of displaying only the longest film from each condition (of 10 measured) is reasonable given the stated reproducibility, but the selection criterion should be more transparent. Were the 10 curves overlaid for all conditions, or only for the representative cases shown? A brief statement of the collapse quality (e.g., RMS deviation) would strengthen the representativeness claim.
  3. §5.3, Fig. 7(b): The salt concentration evolution Cs(t) is derived from the model and not independently measured. The authors are appropriately cautious (stating the model is invalid below 100 nm), but the crosses marking Cs(t*) at h* = 100 nm are presented without uncertainty estimates. A brief note on the sensitivity of Cs(t*) to the fitting parameter a' would help readers gauge the reliability of these values.
  4. Table 2: The fitting parameters a and a' vary across humidities (a: 0.74, 0.67, 0.55; a': 1, 0.7, 0.7, 0.7) without a clear physical explanation for the trend. The authors note that a accounts for deviations from the idealised model, but the systematic decrease of a with increasing humidity is unexplained. A brief comment on whether this trend is physically meaningful or an artifact would be helpful.
  5. §5.1, Eqs. (5.1)–(5.4): The return-map analysis of rupture stochasticity is interesting but somewhat tangential to the central NBF claim. The observation of a negative correlation (315°–135° direction) is reported but not mechanistically interpreted. If the authors cannot offer a physical explanation, a brief acknowledgment that this observation remains unexplained would suffice.
  6. Fig. 9: For Cs° ∈ [65, 97.5] g/L, the authors note that most films attain the 81 mm translation limit, so the displayed curves are not the longest but the longest within this limit. This selection difference should be noted more prominently in the figure caption, not only in the main text.
  7. §4.1: The notation h_p (plateau thickness from single-layer model) vs. h_tot (three-layer total thickness) vs. h† (core thickness) could be confusing. A summary table of the different thickness definitions and their values would improve readability.
  8. The acknowledgment of LLM use is appropriate for transparency. The specific scope (figure style, sentence fluidity) is adequately disclosed.

Simulated Author's Rebuttal

2 responses · 0 unresolved

The referee raises a single major comment concerning whether the ~5 nm thickness plateau attributed to Newton Black Film formation could be an artifact of the interferometric measurement reaching its sensitivity floor at low optical path differences. We agree this is a legitimate and important concern and will address it by including representative raw reflectance spectra from the plateau phase alongside fitted model spectra in a supplementary figure.

read point-by-point responses

  1. Referee: §4.1, Fig. 3(b): The central claim of NBF stabilisation at ~5 nm rests on interferometric thickness measurements at the stated lower limit of the method (5 nm, σ = ±1 nm). At h ≈ 5 nm, the round-trip optical path difference is ~10 nm, corresponding to λ/45–λ/80 of the measured wavelength range (450–800 nm), where reflectance spectra become nearly flat and thickness extraction is ill-conditioned. The paper mitigates this with the three-layer Duyvis model (Eq. 4.1) yielding h† ≈ 0.52 nm consistent with neutron scattering, and the force sensor independently confirms film survival during the plateau. However, the concern is not fully resolved: if the spectrometer returns near-constant reflectance below some threshold, the fitting pipeline could produce an apparent plateau at a fixed thickness that is actually a measurement floor. To fully close this issue, the authors should include at least

    Authors: We thank the referee for this careful and well-taken comment. The concern that the ~5 nm plateau could reflect a measurement floor rather than a genuine physical thickness is entirely legitimate, and we agree it should be addressed directly with raw spectral data. revision: yes

  2. Referee: one representative raw reflectance spectrum from the plateau phase (alongside the fitted model spectrum) in a supplementary figure, demonstrating that meaningful spectral variation is present at h ≈ 5 nm and that the thickness extraction is not degenerate. This is the single most load-bearing point for the central claim and should be addressable within the manuscript scope.

    Authors: We will include a representative raw reflectance spectrum acquired during the plateau phase, alongside the fitted model spectrum, in a supplementary figure. We can confirm that meaningful spectral variation is present at h ≈ 5 nm: the reflectance spectrum is not flat across the 450–800 nm range, and the fitting pipeline extracts a well-defined thickness from genuine spectral features rather than returning a constant floor value. We will also include, for comparison, a spectrum from the thinning phase at a thickness well above the plateau (e.g., h ≈ 50 nm) to make the spectral contrast clear. We note that several independent lines of evidence already support the physical reality of the plateau: (1) the three-layer Duyvis model yields a core thickness h† ≈ 0.52 nm consistent with neutron scattering data (Simister et al. 1992), which would not be the case if the fitting pipeline were simply returning a degenerate floor value; (2) the force sensor independently confirms that the film remains intact during the plateau phase rather than having ruptured; (3) the plateau thickness of ~5 nm is consistent with NBF thicknesses reported in TFPB measurements (Exerowa et al. 1981; Schulze-Schlarmann et al. 2006); and (4) the plateau is observed across all humidities and multiple salt concentrations, with the plateau lifetime (not just its thickness) varying systematically with humidity. Nevertheless, we agree that the raw spectral evidence is the most direct way to close this issue and will add it as requested. revision: yes

Circularity Check

0 steps flagged

No significant circularity. The central NBF observation is a direct experimental measurement, and the evaporation model uses physically-derived expressions with O(1) fit parameters.

full rationale

The paper's central claim — that salt stabilises a Newton black film at ~5 nm — is a direct interferometric observation (Fig. 3b, Fig. 10), not a quantity derived from a fitted model. The evaporation model (§5.2–5.3, Eqs. 5.5–5.10) uses physically-derived expressions for the evaporation rate j_e based on the Grashof number and natural convection (Boulogne & Dollet 2018), with a single O(1) prefactor a (or a') as a fit parameter. The drainage rate j_d is extracted directly from the saturated-atmosphere experimental curve (where j_e = 0 by definition), not from a self-referential definition. The salt concentration evolution C_s(t) (Eq. 5.8) is derived from a mass balance and solved numerically; it is not defined in terms of the output it claims to predict. The three-layer Duyvis model (Eq. 4.1) refines the plateau thickness using independently measured refractive indices and literature values for surfactant layer thickness (Simister et al. 1992), yielding h† ≈ 0.52 nm consistent with neutron scattering — an external check. The self-citation to Ziapkoff et al. (2026) for the optifik thickness measurement method is a methodological reference, not a load-bearing premise for the physical conclusions; the method's validity rests on its own independent calibration. No step in the derivation chain reduces to its inputs by construction. The model's predictions (thinning curves in Fig. 6, 7) are compared against experimental data rather than being definitions of that data. The one minor concern is that the humidity-independent drainage assumption (§5.2) is an unverified approximation, but this is a modeling assumption, not a circularity. Score 2 reflects the methodological self-citation which is not load-bearing for the central claim.

Axiom & Free-Parameter Ledger

4 free parameters · 4 axioms · 0 invented entities

No new entities, particles, forces, or dimensions are postulated. The paper works entirely within the established DLVO framework and standard soap film physics.

free parameters (4)
  • a = 0.74, 0.67, 0.55 for Rh = 40, 60, 80%
    Prefactor in the evaporation rate expression (Eq. 5.7) accounting for deviations from the idealised natural convection model (geometry, thermal exchange, concentration gradients). Fitted to match thinning curves.
  • a' = 1.0, 0.7, 0.7, 0.7 for Rh = 40, 60, 80, 100%
    Prefactor in the salt-modified evaporation rate (Eq. 5.10), analogous to a but for the saline system. Fitted to match thinning curves with salt.
  • L = 20 mm
    Characteristic vertical length scale for the Grashof number (Eq. 5.6). Chosen as a representative film length; the paper does not justify this specific value beyond stating it as the characteristic scale.
  • h_initial = 3.2 μm
    Starting thickness for numerical integration of Eq. 5.5, taken as the first detectable thickness in reference data.
axioms (4)
  • domain assumption Drainage rate jd is independent of atmospheric humidity.
    Stated in §5.2: 'jd is the drainage rate inside the film, supposed independent of the atmospheric humidity.' Used to extract evaporation rates by subtracting the saturated-atmosphere curve. Physically motivated but not independently verified for this system.
  • domain assumption Film thickness is uniform at the measurement point.
    Stated in §5.2: 'we make the hypothesis that the film thickness is uniform.' The optical fiber measures a 400 μm spot at the top of the film; local thickness variations (thick patches) are acknowledged but not accounted for in the model.
  • domain assumption Natural convection dominates evaporative transport (Gr >> 1).
    Computed Gr > 200 across all conditions (§5.2), supporting the use of the Boulogne & Dollet (2018) convection model. The calculation is self-contained and does not depend on the target result.
  • standard math The 5 nm plateau corresponds to a Newton Black Film stabilised by steric repulsion.
    Identification based on thickness matching literature values for NBF (5–10 nm, Schulze-Schlarmann et al. 2006) and the known effect of salt on NBF formation (Exerowa et al. 1981). Standard DLVO framework.

pith-pipeline@v1.1.0-glm · 19521 in / 5670 out tokens · 276430 ms · 2026-07-08T08:15:48.665423+00:00 · methodology

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read the original abstract

We investigate the effect of a high concentration (32.5 g.L$^{-1}$) of sodium chloride (NaCl) on TTAB (tetradecyltrimethylammonium bromide) vertical soap films also called foam films, pulled out of a bath under controlled humidity conditions. We observe that the film lifetime increases with relative humidity, both in the presence and absence of salt. At any given humidity, the presence of NaCl systematically enhances film stability. Our film thickness measurements show that the thinning dynamics with or without salt are nearly identical down to 100 nm. Down to that thickness, the effect of evaporation can be rationalised by a constant evaporation rate, which becomes non-negligible compared to the drainage rate at film thicknesses below 400 nm. The main effect of salt is the stabilisation of a Newton black film at a thickness of approximately 5~nm, whereas in the absence of salt, the film ruptures upon reaching a critical thickness of about 10 nm.

Figures

Figures reproduced from arXiv: 2607.06363 by Anniina Salonen, Emmanuelle Rio, Fran\c{c}ois Boulogne, Victor Ziapkoff.

Figure 1
Figure 1. Figure 1: (a) Set-up scheme of a film generated by translating the reservoir downwards at constant velocity. The force sensor detects the film rupture, and the optical fiber measures the spectrum of the light reflected by the thin film close to the top. The figure exhibits two typical examples of spectra with wavelengths λ ∈ [400, 800] nm. (b) Photograph of a foam film pulled out of a bath. enclosed in a box of dime… view at source ↗
Figure 2
Figure 2. Figure 2: Lifetime τf of TTAB films for relative humidities Rh ∈ [40, 60, 80, 100] % represented in blue, green, yellow, red, respectively, for baths with (a) and without (b) the addition of 32.5 g.L −1 NaCl. (c) Violin plots of the film lifetime distributions, using the same colour code. The label ’NaCl’ indicates experiments performed with salt. The shaded region corresponds to lifetimes where the translation stag… view at source ↗
Figure 3
Figure 3. Figure 3: Time evolution of film thickness for the most stable TTAB film at each relative humidity tested (Rh = 40 %, 60 %, 80 %, 100 %; blue, green, yellow, red), (a) without (▲) salt and (b) with (□) 32.5 g.L −1 NaCl. Insets show the data in log-lin scale. [h] 5 10 15 20 25 t [s] 0 1000 2000 3000 h [nm] 20 40 60 t [s] 0 1000 2000 3000 h [nm] 20 40 60 t [s] 0 2000 4000 h [nm] 20 40 60 t [s] 0 2000 h [nm] 10 20 101 … view at source ↗
Figure 4
Figure 4. Figure 4: Thinning curves of films with (□) and without (▲) 32.5 g.L −1 NaCl for the four fixed relative humidities: (a) Rh = 40 %, (b) Rh = 60 %, (c) Rh = 80 %, and (d) Rh = 100 %. The ▲ markers for films without salt are outlined in black for clarity. Insets show the data in log-lin scale. (a), (b), (c), and (d), respectively. Each figure includes an inset representing the data in log-lin scale. In [PITH_FULL_IMA… view at source ↗
Figure 5
Figure 5. Figure 5: (a) Experimental return maps for films without salt at four relative humidities Rh ∈ [40, 60, 80, 100] %. (b) Experimental return maps for films with 32.5 g.L −1 sodium chloride addition under identical humidity conditions. Polar representation of the variance ⟨zi(θ) 2 ⟩ as a function of the angle θ for films (c) without salt and (d) with salt addition, at relative humidities Rh ∈ [40, 60, 80, 100] %. All … view at source ↗
Figure 6
Figure 6. Figure 6: Time shifted evolution of film thickness for the TTAB film showed in [PITH_FULL_IMAGE:figures/full_fig_p011_6.png] view at source ↗
Figure 7
Figure 7. Figure 7: (a) Time shifted evolution of the film thicknesses for TTAB films with salt shown in [PITH_FULL_IMAGE:figures/full_fig_p013_7.png] view at source ↗
Figure 8
Figure 8. Figure 8: (a) Illustration of the three characteristic times, the film lifetime τf , the thinning lifetime τt and the plateau lifetime τp for a thinning curve obtained with C ◦ s = 32.5 g.L −1 NaCl at a relative humidity of Rh = 80 %. The inset shows the determination of τt from the plot of 1/h versus t (log-lin scale). (b) Mean film lifetime, ⟨τf ⟩, as a function of the mean thinning time, ⟨τt⟩, for all relative hu… view at source ↗
Figure 9
Figure 9. Figure 9: Thinning curves of films in [PITH_FULL_IMAGE:figures/full_fig_p015_9.png] view at source ↗
Figure 10
Figure 10. Figure 10: Mean film thickness ⟨hp⟩ averaged over the plateau once local thickening is no longer observed in the thinning curves in [PITH_FULL_IMAGE:figures/full_fig_p016_10.png] view at source ↗
Figure 11
Figure 11. Figure 11: Surface tension as a function of TTAB concentration with (×) and without (×) the addition of 32.5 g.L−1 of NaCl. REFERENCES Auregan, T & Deike, L ´ 2024 Drainage and lifetime of thin liquid films: The role of salinity and convective evaporation. arXiv . Bergeron, V 1997 Disjoining pressures and film stability of alkyltrimethylammonium bromide foam films. Langmuir 13 (13), 3474–3482. Boulogne, F. 2019 Chea… view at source ↗

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