Next Article in Journal
The Temperature-Dependent Tight Binding Theory Modelling of Strain and Composition Effects on the Electronic Structure of CdSe- and ZnSe-Based Core/Shell Quantum Dots
Previous Article in Journal
Investigation of the Effect of the Shape of Cutting Knives Limiting Burr in High-Strength Multiphase Steel Sheets
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Materials
Volume 18
Issue 2
10.3390/ma18020281
materials-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Communication

Innovative Supported Membranes for Ion Mobility Spectrometer (IMS) Sample Introduction Systems with High Permeability Relative to Toxic Agents in Air (TAAs)

by
Monika Wiśnik-Sawka
*,
Wojciech Fabianowski
* and
Dorota Gajda
Military Institute of Chemistry and Radiometry, gen A. Chruściela “Montera” 105, 00-910 Warsaw, Poland
*
Authors to whom correspondence should be addressed.
Materials 2025, 18(2), 281; https://doi.org/10.3390/ma18020281
Submission received: 28 May 2024 / Revised: 8 July 2024 / Accepted: 10 July 2024 / Published: 10 January 2025
(This article belongs to the Section Polymeric Materials)
Browse Figures
Versions Notes

Abstract

:
One of the main objectives of the ion mobility spectrometry (IMS) technique is to reduce moisture in detection systems, which causes the formation of ion clusters and ion water and a reduction in formed clusters’ activity. Thus, one of the methods limiting moisture in a sampling injection system is to use hydrophobic polymeric membranes. The use of membranes with high permeability relative to the analysed organic compounds is required, including toxic agents in air (TAAs). Such requirements align with those of polydimethylsiloxane (PDMS) membranes. Unfortunately, thin PDMS membranes are not mechanically resistant. In this study, relatively thin PDMS membranes were reinforced with fine mesh fabric supports. These supports were chemically modified with selected oligoglycol derivatives and finally coated with PDMS. The obtained membranes were tested for water permeability and TAA simulants.

1. Introduction

Polymeric materials have a wide range of applications in various fields due to their diverse properties. One of the applications of polymers is membrane production, which is used to separate substances between two phases due to their properties [1]. Membrane modification causes an increase or a decrease in permeability with respect to selected substances via polymer structures [2,3].
Toxic agents in air (TAAs) are a group of highly toxic compounds, and their physiological classification is as follows: nerve agents (soman, sarin, tabun, and Vx group), blistering agents (sulphur mustard, nitrogen mustard, and lewisite), blood agents (hydrogen cyanide and cyanogen chloride), and choking agents (phosgene and diphosgene) [4]. Protection from these substances on the battlefield is provided by protective clothing, which comprises a mechanical barrier against the contact of TAAs with the soldier’s body. Research on materials with reduced permeability to TAAs is the subject of a large number of scientific works and patents [5,6,7]. The other method of protection is the fast detection and identification of these compounds at the point of their dispersion. This is particularly important because it constrains contact with toxic substances. Current research is focused on achieving even lower detection thresholds for TAAs.
The ion mobility spectrometry (IMS) technique is characterised by the fast generation of an analytical signal (time constant of several seconds) and continuous operation. The number of organic compounds that could possibly be detected and analysed utilising this technique is large. Hence, IMS has wide applications in forensics and military purposes [8,9,10,11].
IMS detectors are widely utilised for the rapid detection of high-energy materials (HEMs), TAAs, or drugs [8,12,13]. IMS detectors have found applications in both laboratory equipment and portable chemical compound detectors. They are characterised by high sensitivity, with a limit of detection measured in ppb, and short measurement times—less than one minute per whole cycle. For this reason, IMS detectors are also used in analytical laboratories, e.g., for food sample analyses [10,14,15]. Instruments that use the IMS detector can be equipped with a sample introduction system (SIS). Often, a polymer membrane is used as a component of this system. It restricts the access of the analysed gas and components and, in particular, eliminates the access of water vapour to the ionisation tube [16,17,18].
One of the challenges in designing IMS detection systems is to reduce moisture levels that are introduced to the sample injection system. The high level of moisture causes the formation of hydrated ion clusters, which decreases analysed ion clusters and their reactivity. High humidity levels significantly affect the ionisation capacity of the analyte. Water molecules may react with the analyte and form hydrated ion clusters that hinder the detection of organic matter. Moreover, the higher the analyte’s humidity, the lower the intensity of the peak signal [19,20,21].
Applying hydrophobic polymeric membranes in the sample injection system is one of the methods for achieving a reduction in water content in the analyte. Two types of membranes are utilised in the IMS technique: track-etched (TE) membranes and membranes made of polydimethylsiloxane (PDMS). Unfortunately, thin PDMS membranes are not mechanically resistant. To increase mechanical resistance, membranes are reinforced with fine mesh fabric support [22,23].
One approach to lowering the detection threshold for IMS detectors is the usage of polymer membranes in SIS, which not only limit moisture content but are also characterised by increased permeability relative to selected organic compounds. PDMS membranes are widely used in IMS techniques due to their high hydrophobicity and simple membrane modification [12,13,14,15,24,25,26,27,28,29,30].
The process of chemical compound permeation in solid PDMSs is complex and determined by penetrant–polymer interactions [22]. The mechanism of diffusion is based on the accommodation (absorption) of the penetrant and the creation of voids to ensure that the penetrant can pass through, i.e., be transported in the polymer [23].
The interaction of water with PDMS has been extensively discussed, particularly in terms of the statistical–mechanical binding theory of water molecules and the theory of water polycondensation [22,31,32,33,34,35,36,37,38,39,40]. In the case of water, single-molecule diffusion does not always occur. Water undergoes polycondensation, resulting in the diffusion of multimolecular conglomerates in the material.
Studies [22,32] have shown that the diffusion coefficient is closely related to water activity, which is associated with a reduction in water permeation through a PDMS membrane. Banerjee et al. [38,39] have investigated water permeation [38,39,40] and have also investigated permeation for dimethyl methylphosphonate (DMMP) used as a TAA simulant. It was found that at room temperature, water permeates slower than DMMP.
In this study, membrane supports were modified with polydimethylsiloxane (PDMS) and additives. During the research, supports such as irradiated track-etched poly(ethylene terephthalate) (TE-PET) film, Cordura® (Invista, Wichita, KS, USA), nylon, and elastane were investigated. Additionally, the membrane’s properties were modified with additives such as the oligomers of poly(ethylene glycol) (PEG), polypropylene glycol oligomer (PPG), and calix[6]arene to increase TAA permeability. The membranes obtained were subjected to liquid water permeability tests, and their permeability relative to water vapour was also determined. A drift tube ion mobility spectrometer (DT IMS) was applied to measure the number and amount of membrane impurities. The main objective of the studies was to obtain mechanically robust PDMS membranes with limited permeability relative to water and high permeability relative to TAAs. These membranes would be cheaper, attractive alternatives for track-etched membranes, which are widely used in the SIS of IMS detectors.

2. Materials and Methods

2.1. Chemicals

For membrane preparation, polydimethylsilicone PDMS (Sylgard 184, Dow Corning, Midland, MI, United States) and two elastomer components were used [41]. A mixture of hexane (purity 95%, Sigma-Aldrich, St. Louis, MO, US) and isopropanol (ACS reagent, ≥99.5%, Sigma-Aldrich) was used as a solvent for PDMS. Different admixtures were added to this mixture. The admixtures are shown in Table 1.
PDMS polymers are highly hydrophobic, electro-insulating materials, and they are transparent within the UV–Vis range. After cross-linking, they are resistant relative to organic solvents and high temperatures. These polymers are completely inert with regard to human health, which is why they are used in the pharmaceutical or food industry. Membranes made of PDMSs are commonly used for the separation of many organic compounds.
Membranes are characterised by specific parameters, which include the permeability P, solubility S, and the diffusion coefficient D of the compound in the material. The permeability depends on D and S and is described using the following Equation (1):
P = D · S
In order to increase the diffusion coefficient, relatively thin PDMS membranes are required. These membranes must maintain mechanical strength and resistance to varying pressures [42,43]. Several different methods can be applied for the preparation of thin PDMS membranes, including Langmuir–Blodgett transfer (LBT) [44,45,46], casting a drop of a polymer solution onto a water surface [47,48,49,50], or casting drops from dilute solutions.
The solubility of an analysed compound in a polymer material can be increased by adding admixtures. These can be organic substances or inorganic molecules dissolved in the polymer or those incorporated into the polymer structure. The admixtures must demonstrate chemical similarity to the tested compounds.
In the first step of the research, the properties of thin PDMS membranes cast from dilute solutions onto thin, porous grids were tested as reinforcing supports. These supports should allow the obtainment of thin PDMS membranes with thicknesses of a few micrometres. Moreover, the obtained membrane must be relatively mechanically robust.
All supports were carefully washed with a mixture of hexane and isopropanol prior to PDMS solution casting. Subsequently, they were dried at 40℃ and placed on a levelled glass plate.
The membrane’s properties were characterised by chemicals such as the following: betanin (red beetroot extract diluted with dextrin) (Aldrich) and TAA simulants: dipropylene glycol monomethyl ether (DPMG) (mixture of isomers for synthesis, Millipore); dimethyl methylphosphonate (DMMP) (purity ≥ 97%, Sigma-Aldrich); and methyl salicylate (MS) (purity ≥ 99%, Sigma-Aldrich).

2.2. Membrane Preparation

2.2.1. Membrane Supports

Four supports were used for membrane preparation: TE-PET film, Cordura®, elastane fabrics, and nylon.
Poly(ethylene terephthalate) (PET) films were irradiated with accelerated Kr ions (energy E of 250 MeV) and subsequently etched with acids (these films were delivered by the Institute of Chemistry and Nuclear Technology (INCT), Warsaw, Poland). The utilised technique made it possible to produce primers with different pore diameters: 0.2, 0.4, 1.0, and 1.3 µm (Figure 1a,b).
Cordura® (Dow Corning) [51] (Figure 1c,d) is an abrasion-resistant fabric made of polyamides, with a polyurethane coating primed with Teflon.
The elastane fabrics comprise polyether–polyurethane copolymers (The Lycra Company, Wilmington, DE, USA) [52] (Figure 1e,f).
Nylon [53] comprised 63% polyamide and 37% elastane (Ferax Sp. z o.o.), with fabric weave thicknesses of 15 and 8 den.
TE-PET film and Cordura® were cut into 6 cm × 6 cm squares. Elastane fabrics and nylon were cut into 5.5 cm × 5.5 cm squares. All supports were placed on a levelled glass plate, and a PDMS/hexane solution was applied using a syringe. This method allowed for the covering of these supports with a controlled volume of applied solution and thorough distributions over the surface. After 24 h of drying at room temperature, the membranes were placed in an oven (120 °C) for 2 h.

2.2.2. Membrane Characterisation

Table 2 shows data on the prepared PDMS/support membranes. The membranes’ thicknesses were calculated using Equation (2) [41]:
d m = Δ m ρ P D M S A
where dm denotes the thickness of membranes [cm]; Δm denotes a change in support mass [g]; ρPDMS denotes the PDMS density [1.03 g/cm3]; and A denotes the support area [cm2].
Nylon with weave thicknesses of 8 and 15 denier was used to prepare doped membranes. The PDMS layer was modified via PEG or PPG with different molecular weights or via Calixarene. PDMS membranes with additives were prepared by mixing an isopropanol solution of PEG, PPG, and Calixarene with a hexane polysilicon solution in a weight ratio of 1:5 and poured onto the selected microporous support mesh. The diversity in membrane thickness was obtained by changing the volume (1–5 cm3) of the casting solution: 25% w/w PDMS/hexane solution or 2.8% w/w PDMS/hexane solution. Membrane data are shown in Table 3. Membrane thicknesses were determined in the same manner as for undoped membranes.

2.3. Experimental Methods

2.3.1. Membrane Leakage Test

The obtained PDMS membranes were tested for permeability relative to liquid water in a simple laboratory procedure (Figure 2). The flat membranes were placed in a rack’s windows. In the next step, the rack was placed on a white sheet of paper. A betanin solution was applied to each of the tested membranes. The areas of the applied solution were determined. After 5 min, the rack was removed from the sheet of paper and traces from the red dye were observed. The tightness of the membrane was defined as the ratio of the area of the stain on the paper (AS) to the area of the dye applied to the membrane (AD).

2.3.2. Gas Permeability

The tight membranes were tested relative to water vapour levels and TAA permeability. In this research, a variation of the ASTM E96 method, e.g., the upright cup method, was used [54]. The investigated membrane was placed in the cap to cover the hollow space. In the first stage, the vials were filled with 5 mL of water. The vial was twisted and weighed. Subsequently, the vials were left in an incubator at 25 °C. The samples were weighed at different times. This experiment allowed for the determination of the mass loss curve.
These modified membranes were characterised using a static method. Such a solution is commonly used to prepare permeation standards used to obtain calibration curves for the IMS detector under study [55,56,57].

2.3.3. Membrane’s Self-Cleaning

Moreover, the membrane’s ability to clean itself with airflow was investigated. Ion mobility spectrometry was utilised to observe impurity removal from the tested membranes. Figure 3 shows the membrane self-cleaning system.
An ion mobility spectrometer with a drift tube was used as a rapid analysis element (the detector was designed and commissioned at the Military Institute of Chemistry and Radiometry). To ensure that the membrane was washed with clean air, an activated carbon filter was connected to the inlet of the diffusion cell. The composition of the permeate was analysed continuously in the IMS detector.

2.3.4. Membrane Permeability Relative to TAA

The membrane’s permeability relative to TAA was observed using the colorimetric method, which is utilised for TAA identification in the Armed Forces. The simulants are a group of compounds with similar physicochemical properties to TAAs; fortunately, they do not exhibit such high toxicity.
For the simulants, three chemicals were chosen:
-
DPMG and MS as H-type blister agents (simulation of sulphur mustard);
-
DMMP as a G-type nerve agent (simulation of phosphoroorganic TAAs such as tabun, sarin, or soman).
The investigated membrane was placed into the cap to cover a hollow. One drop of the DPMG, MS, or DMMP (0.5 cm3) was placed inside the vial and capped with a membrane stopper. TAA was detected using a paper chemical agent detector (indicator paper—3-way liquid, adhesive-backed No. 6665-21-858-8494). The paper was cut and placed onto a Petri dish. The vial and Petri dish were placed in a desiccator. The degree of permeation was tested by taking a photo of the paper. The analysis was carried out based on photographs taken at specific time intervals. The photographs were subjected to colour analyses in a graphics programme. The colour change was determined by determining the values of the colour components red (R), green (G), blue (B), hue (H), saturation (S), and value (V), which were determined from several points in the photo. Based on the values, a colour was generated, which is illustrated in the last column of the Table 4. Due to the many components, the colour change analysis was carried out based on the observation of the generated colour.

3. Results

In Figure 4, data for the liquid water permeability testing of PDMS membranes cast on different supports are presented. If there were any dye spots on a sheet of paper after membrane removal, the AS/AD ratio was determined; if AS = 0, the membrane did not experience leakage. An As value higher than 0 excludes a membrane’s further use in this research.
The most promising results were obtained for TE-PET membranes with pore sizes of 1.0 µm and 1.3 µm, which were modified with 2 or 4 mL of PDMS/hexane 10% w/w solution and all elastane- and nylon-reinforced membranes. Because TE-PET membranes were treated only as reference membranes, they were not tested in the subsequent research study. The Cordura®-supported membrane was highly permeable relative to water in tests with an aqueous solution of betanin (red dye). It is likely that the primers were poorly wetted with the polymer solution. This phenomenon may have caused the membrane’s leakage. All elastane and nylon membranes were tight; thus, they were tested for water vapour permeability. The results of the permeability to water vapour test are shown in Figure 5. During the measurement, the loss of the vial’s weight over time was recorded.
The same tests were carried out for membranes supported with elastane and 15-denier nylon.
The time dependence of water mass loss allows the determination of the permeability expressed in terms of the amount of water vapour passing through a unit area of membrane per unit time. Figure 6 shows the calculated water vapour penetration values for different membrane thicknesses.
The thickness of PDMS/elastane membranes was within the range of 100 μm to 400 μm. The research showed that for these membranes, water vapour permeability decreases from 0.12 to 0.37 gcm−2h−1. An increase in membrane thickness causes a decrease in permeability relative to water.
The thicknesses of PDMS/nylon membranes were within the range of 3.4 to 8.6 μm. For these membranes, the change in thickness was not substantial; therefore, permeability for each membrane was at similar levels—0.34 to 0.415 gcm−2h−1.
The permeability value for water vapour was also determined for doped membranes. Changes in weight values over time for membranes on 8 den nylon and 15 den supports are shown in Figure 7.
The membranes obtained were characterised via a constant water vapour permeation value, as shown in Figure 5 and Figure 7. The water vapour concentration over the membrane was constant due to the stability of water emissions from the vial.
For the membranes supported via 8 den nylon, the permeability to water vapour was reduced only for the 8PEG600 membrane (Figure 8a). For the membranes modified with Calixarene, the permeability to water was even higher than for the undoped reinforced membrane itself. For the membrane supported with 15-denier nylon (Figure 8b), the addition of PPG400 increases the permeability to water. No significant change in permeation was observed for other admixtures. It is worth noting that the addition of PEG, PPG, or Calixarene has an influence on the water vapour permeability (WVP) value (Figure 8).
Two membranes—8PEG600 and Nyl15—were tested with respect to their airflow self-cleaning ability. For this purpose, a system with an ion mobility spectrometer was applied (Figure 3). Each membrane tested was mounted in the diffusion cell of the system, and the drift time spectrum was recorded as soon as the measurement began. The results of the experiment are shown in Figure 9.
Both membranes were heavily contaminated and were therefore cleaned in an air stream for approximately 100 h. The membrane modified with 8PEG600 was almost impurity-free; for that reason, it was applied in further tests.
The 8PEG600 membrane was selected for the permeability studies of DPMG, MS, and DMMP. This membrane was chosen because of its low water vapour permeability and strength. The results of the study are shown in Table 4.
Research on permeability relative to TAAs was carried out analogically compared to permeability relative to water. Indicator papers are the simplest means used for the detection of the presence of poisonous TAAs during military operations (including on the battlefield during wartime). The biggest advantage of using indicator papers is that they are relatively easy to use. The change in colour of the paper provides the soldier with clear and legible information about the dispersion of poisonous substances in the surrounding atmosphere. The colour change analysis is described in Section 2.3.4. The values of the colour components are shown in Table 4. Regrettably, indicator papers have relatively low sensitivity; nevertheless, they are accepted by the Armed Forces as an indicator for the preliminary detection of TAAs.
Permeability tests for DPMG, MS, and DMMP were carried out in a similar manner as for water. A drop of DPMG, MS, or DMMP (0.5 cm3) was deposited at the vial’s bottom, and the investigated membrane was placed in the vial cup. The indicator’s paper was located on the cup’s surface. Taking into account the very low vapour pressure of the tested MS (14.8 Pa [58]), DMMP (<0.1 Pa [59]), and DPMG (53.3 Pa [60]) compared to a water vapour pressure of VP = 3169 Pa [61], the change in the vial’s mass could be registered after several dozen hours. For this reason, research on DPMG, MS, and DMMP permeability was carried out using indicator papers.
TAA colorimetric indices showed colour changes after exposure to all tested DPMG, MS, and DMMP pairs. For MS, the most intense colour occurred up until 240 h; nevertheless, the indicator paper began to redden just after 24 h. DMMP and MS caused a change in colour within 24–72 h. The colouration obtained for DPMG occurred rapidly. Any intensity change in colour was not registered after 24 h.
Taking into account the very low vapour pressure of the tested simulants of TAAs and the appearance of the colour reaction on the indicator, these observations prove that the selected membrane permeability increased after modification, and it was high for all tested DPMG, MS, and DMMP.

4. Conclusions

This research study focused on finding more cost-effective and attractive membranes, compared to track-etched membranes that are produced only by the Joint Institute for Nuclear Research in Dubna (irradiated in Dubna and etched with acids at the Institute of Nuclear Chemistry and Technology, Warsaw, Poland). Given the scarcity of the alternative membranes, the purchase of track-etched membranes is currently almost impossible.
Three supports were selected (Cordura®, nylon, and elastane) for further modification with PDMS in order to obtain waterproof and mechanically robust membranes.
Studies have shown that there is no justification for modifying Cordura® material. This material is airtight and hydrophobic, but it loses its properties and becomes permeable relative to water after applied modifications. In the case of unmodified membranes, the most promising results were observed for membranes supported with elastane and nylon. After PDMS modification, these supports were waterproof.
Apart from pure PDMS, chosen supports were also modified with a mixture of PDMS with additives (PEG, PPG, and calix[6]arene) to increase TAA permeability.
The thickness of PDMS/nylon was within the range of 3.4 to 8.6 µm, and in this range, changes in water vapour permeability have not been observed. PDMS/elastane membranes were thicker, and significant changes in water permeability within the membrane thickness range of 100 µm to 400 µm were observed.
Of all modified membranes, the most effective was 8PEG600, for which the lowest degree of water vapour permeability was observed. This membrane also exhibited the highest self-cleaning ability.
Preliminary tests performed for DPMG, MS, and DMMP using the indicator papers showed that the selected membrane exhibits increased permeability relative to TAAs. This is due to the fact that the sensitivity of papers for simulants is lower than for TAAs.
In a PhD thesis, the emissions of DMMP through pure PDMS membranes, which appeared after 100 h (35 °C) in static conditions, were described [62]. This is why we can conclude that the obtained membrane (PDMS with PEG, reinforced with 8 den nylon) is characterised by its higher permeability relative to DMMP: the emissions of DMMP through the modified membrane appear after 24 h (25 °C) in static conditions.
This study proved that nylon used as a support could be a low-cost, readily available material that can provide adequate backing for the membrane with respect to specific membrane properties. This study presents results that could become a significant foundation for research on materials with increased permeability relative to highly toxic substances such as TAAs.

Author Contributions

Conceptualisation, W.F.; methodology, W.F.; validation, W.F. and M.W.-S.; formal analysis, M.W.-S.; writing—original draft preparation, W.F. and M.W.-S.; writing—review and editing, M.W.-S. and D.G.; visualisation, M.W.-S. and D.G.; supervision, W.F.; project administration, W.F. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the Military Institute of Chemistry and Radiometry, grant no. 3/2021.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

Data are unavailable due to privacy.

DURC Statement

Current research is limited to the material science and chemical engineering, which is beneficial for future design of equipment for first responders and does not pose a threat to public health or national security. Authors acknowledge the dual use potential of the research involving preparation of innovative supported membranes and confirm that all necessary precautions have been taken to prevent potential misuse. As an ethical responsibility, authors strictly adhere to relevant national and international laws about DURC. Authors advocate for responsible deployment, ethical considerations, regulatory compliance, and transparent reporting to mitigate misuse risks and foster beneficial outcomes.

Acknowledgments

Institute of High Pressure, Polish Academy of Science, Warsaw, Poland.

Conflicts of Interest

The authors declare no conflicts of interest.

References

  1. Koros, W.J.; Ma, Y.H.; Shimidzu, T. Terminology for membranes and membranę processes. Pure Appl. Chem. 1996, 68, 1479–1489. [Google Scholar] [CrossRef]
  2. Drioli, E.; Giorno, L. (Eds.) Encyclopedia of Membranes; Springer: Berlin/Heidelberg, Germany, 2016. [Google Scholar]
  3. Hoek, E.M.V.; Tarabara, V.V. Encyclopedia of Membrane Science and Technology; John Wiley and Sons Ltd.: Hoboken, NJ, USA, 2013. [Google Scholar]
  4. Munro, N.B.; Talmage, S.S.; Griffin, G.D.; Waters, L.C.; Watson, A.P.; King, J.F.; Hauschild, V. The sources, fate, and toxicity of chemical warfare agent degradation products. Environ. Health Perspect. 1999, 107, 933974. [Google Scholar] [CrossRef] [PubMed]
  5. Steinberg, R.S.; Cruz, M.; Mahfouz, N.G.A.; Qiu, Y.; Hurt, R.H. Breathable Vapor Toxicant Barriers Based on Multilayer Graphene Oxide. ACS Nano 2017, 11, 5670–5679. [Google Scholar] [CrossRef] [PubMed]
  6. Eliseev, A.A.; Poyarkov, A.A.; Chernova, E.A.; Eliseev, A.A.; Chumakov, A.P.; Konovalov, O.V.; Petukhov, D.I. Operando study of water vapor transport through ultra-thin graphene oxide membranes. 2D Mater. 2019, 6, 035039. [Google Scholar] [CrossRef]
  7. Peng, C.; Iqbal, Z.; Sirkar, K.K.; Peterson, G.W. Graphene Oxide-Based Membrane as a Protective Barrier against Toxic Vapors and Gases. ACS Appl. Mater. Interfaces 2020, 12, 11094–11103. [Google Scholar] [CrossRef] [PubMed]
  8. Eiceman, G.A.; Karpas, Z. Ion Mobility Spectrometry, 2nd ed.; CRC Press: Boca Raton, FL, USA, 2005. [Google Scholar]
  9. Sorribes-Soriano, A.; de la Guardia, M.; Esteve-Turrillas, F.A.; Armenta, S. Trace analysis by ion mobility spectrometry: From conventional to smart sample preconcentration methods. A review. Anal. Chim. Acta 2018, 1026, 37–50. [Google Scholar] [CrossRef] [PubMed]
  10. Budzyńska, E.; Sielemann, S.; Puton, J.; Surminski, A.L.R.M. Analysis of e-liquids for electronic cigarettes using GC-IMS/MS with headspace sampling. Talanta 2020, 209, 120594. [Google Scholar] [CrossRef]
  11. Yanini, A.; Esteve-Turrillas, F.A.; de la Guardia, M.; Armenta, S. Ion mobility spectrometry and high-resolution mass-spectrometry as methodologies for rapid identification of the last generation of new psychoactive substances. J. Chromatogr. A 2018, 1574, 91–100. [Google Scholar] [CrossRef] [PubMed]
  12. Eiceman, G.A. Ion-mobility spectrometry as a fast monitor of chemical composition. Trends Anal. Chem. 2002, 21, 259–275. [Google Scholar] [CrossRef]
  13. Stach, J.; Baumbach, J.I. Ion mobility spectrometry—Basic elements and applications. Int. J. Ion Mobil. Spectrom. 2002, 5, 1–21. [Google Scholar]
  14. Capitain, C.; Weller, P. Non-Targeted Screening Approaches for Profiling of Volatile Organic Compounds Based on Gas Chromatography-Ion Mobility Spectroscopy (GC-IMS) and Machine Learning. Molecules 2021, 26, 5457. [Google Scholar] [CrossRef] [PubMed]
  15. Yin, J.; Wu, M.; Lin, R.; Li, X.; Ding, H.; Han, L.; Yang, W.; Song, X.; Li, W.; Qu, H.; et al. Application and development trends of gas chromatography–ion mobility spectrometry for traditional Chinese medicine, clinical, food and environmental analysis. Microchem. J. 2021, 168, 106527. [Google Scholar] [CrossRef]
  16. Arce, L.; Valcárcel, M. Membrane Set up Combined with Photoionization-Ion Mobility Spectrometer to Improve Analytical Performance and Avoid Humidity Interference on the Determination of Aromatics in Gaseous Samples. J. Chromatogr. A 2016, 1431, 55–63. [Google Scholar]
  17. Du, Y.; Zhang, W.; Whitten, W.; Li, H.; Watson, D.B.; Xu, J. Membrane-Extraction Ion Mobility Spectrometry for in Situ Detection of Chlorinated Hydrocarbons in Water. Anal. Chem. 2010, 82, 4089–4096. [Google Scholar] [CrossRef] [PubMed]
  18. Holopainen, S.; Nousiainen, M. Determination of Fuel Ethers in Water by Membrane Extraction Ion Mobility Spectrometry. Talanta 2013, 106, 448–453. [Google Scholar] [CrossRef] [PubMed]
  19. Holopainen, S.; Nousiainen, M.; Anttalainen, O.; Sillanpa, M.E.T. Sample-Extraction Methods for Ion-Mobility Spectrometry in Water Analysis. Trends Anal. Chem. 2012, 37, 124–134. [Google Scholar] [CrossRef]
  20. Borsdorf, H.; Fiedler, P.; Mayer, T. The effect of humidity on gas sensing with ion mobility spectrometry. Sens. Actuators B Chem. 2015, 218, 184–190. [Google Scholar] [CrossRef]
  21. Mäkinen, M.; Sillanpää, M.; Viitanen, A.; Knap, A.; Mäkelä, J.M.; Puton, J. The effect of humidity on sensitivity of amine detection in ion mobility spectrometry. Talanta 2011, 84, 116–121. [Google Scholar] [CrossRef]
  22. Barrie, J.A.; Machin, D. The sorption and diffusion of water in silicone rubbers. Part I Unfilled rubbers. J. Macromol. Sci. Phys. B 1969, 3, 645–672. [Google Scholar] [CrossRef]
  23. Frisch, H.L.; Stern, S.A. Diffusion of small molecules in polymers. Crit. Rev. Solid State Mater. Sci. 1984, 11, 123–187. [Google Scholar] [CrossRef]
  24. Borsdorf, H.; Schelhorn, H.; Flachowsky, J.; Döring, H.R.; Stach, J. Corona discharge ion mobility spectrometry of aliphatic and aromatic hydrocarbons. Anal. Chim. Acta 2000, 403, 235–242. [Google Scholar] [CrossRef]
  25. Borsdorf, H.; Nazarov, E.G.; Miller, R.A. Time-of-flight ion mobility spectrometry and differential mobility spectrometry: A comparative study of their efficiency in the analysis of halogenated compounds. Talanta 2007, 71, 1804–1812. [Google Scholar] [CrossRef] [PubMed]
  26. Kotiaho, T.; Lauritsen, F.R.; Degn, H.; Paakkanen, H. Membrane inlet ion mobility spectrometry for on-line measurement of ethanol in beer and in yeast fermentation. Anal. Chim. Acta 1995, 309, 317–325. [Google Scholar] [CrossRef]
  27. Baumbach, J.I.; Sielemann, S.; Xie, Z.; Schmidt, H. Detection of the gasoline components methyl tert-butyl ether, benzene, toluene, and m-xylene using ion mobility spectrometers with a radioactive and UV ionization source. Anal. Chem. 2003, 6, 1483–1490. [Google Scholar] [CrossRef] [PubMed]
  28. Borsdorf, H.; Rämmler, A. Continuous on-line determination of methyl tert-butyl ether in water samples using ion mobility spectrometry. J. Chromatogr. A 2005, 1072, 45–54. [Google Scholar] [CrossRef] [PubMed]
  29. Kou, D.; San Juan, A.; Mitra, S. Gas injection membrane extraction for fast on-line analysis using GC detection. Anal. Chem. 2001, 73, 5462–5467. [Google Scholar] [CrossRef] [PubMed]
  30. Higgins, B.; Simonson, D.; McGill, R.A.; Nguyen, V.; Stepnowski, J.; Pai, R.; Stepnowski, S.; Rake, M. Functionalized Sorbent Membranes for Use with Ion Mobility Spectrometry. In Proceedings of the 2008 IEEE Conference on Technologies for Homeland Security Conference Committees, 2008 IEEE Conference on Technologies for Homeland Security, Waltham, MA, USA, 12–13 May 2008; pp. 139–143. [Google Scholar]
  31. King, G. Permeability of keratin membranes to water vapour. Trans. Faraday Sot. 1945, 41, 479–487. [Google Scholar] [CrossRef]
  32. Favre, E.; Schaetzel, P.; Nguyen, Q.T.; Clement, R.; Neel, I. Sorption, diffusion and vapour permeation of various penetrants through dense poly (dimethylsiloxane) membranes: A transport analysis. J. Membr. Sci. 1994, 92, 169–184. [Google Scholar] [CrossRef]
  33. Watson, J.M.; Baron, M.G. The behaviour of water in poly(dimethylsiloxane). J. Membr. Sci. 1996, 110, 47–57. [Google Scholar] [CrossRef]
  34. Wong, W.S.Y.; Hauer, L.; Naga, A.; Kaltbeitzel, A.; Baumli, P.; Berger, R.; D‘Acunzi, M.; Vollmer, D.; Butt, H.J. Adaptive Wetting of Polydimethylsiloxane. Langmuir 2020, 36, 7236–7245. [Google Scholar] [CrossRef]
  35. Taylor, R.L.; Herrmann, D.B.; Kemp, A.R. Diffusion of water through insulating materials. Ind. Eng. Chem. 1936, 28, 1255–1263. [Google Scholar] [CrossRef]
  36. Akhtar, F.H. Water Vapor Separation: Development of Polymeric and Mixed-Matrix Membranes, Rozprawa Doktorska, 2019, King Abdullah University of Science and Technology Thuwal, Kingdom of Saudi Arabia. dostęp dnia 24.06.2022. Available online: https://repository.kaust.edu.sa/bitstream/handle/10754/631897/Faheem_PhD_Thesis.pdf?sequence=4 (accessed on 24 June 2022).
  37. Barrie, J.A.; Platt, B. The diffusion and clustering of water vapour in polymers. Polymer 1963, 4, 303–313. [Google Scholar] [CrossRef]
  38. Banerjee, S.; Asrey, R.; Vyas, K.D.; Bhattacharya, A. Quartz piezoelectric crystal detector for sensing organophosphorus compounds and study of diffusion of chemical pollutants through elastomeric membranes. J. Polym. Mater. 1996, 13, 29. [Google Scholar]
  39. Banerjee, S.; Asrey, R.; Saxena, C.; Vyas, K.; Bhattacharya, A. Kinetics of diffusion of water and dimethylmethylphosphonate through poly(dimethylsiloxane) membrane using coated quartz piezoelectric sensor. J. Appl. Polym. Sci. 1997, 65, 1789–1794. [Google Scholar] [CrossRef]
  40. Almquista, C.B.; Hwang, S.T. The permeation of organophosphorus compounds in silicone rubber membranes. J. Membr. Sci. 1999, 153, 57–69. [Google Scholar] [CrossRef]
  41. Sylgard 184 Dow-Corning Technical Data Sheet. Available online: https://www.farnell.com/datasheets/3154500.pdf (accessed on 24 July 2022).
  42. Abulyazied, D.E.; Ene, A. An investigative study on the progress of nanoclay-reinforced polymers: Preparation, properties and applications: A Review. Polymers 2021, 13, 4401. [Google Scholar] [CrossRef] [PubMed]
  43. Kabakci, G.C.; Aslan, O.; Bayraktar, E. Toughening mechanism analysis of recycled rubber-based composites reinforced with glass bubbles, glass fibers and alumina fibers. Polymers 2021, 13, 4215. [Google Scholar] [CrossRef] [PubMed]
  44. Blodgett, K.B. Monomolecular films of fatty acids on glass. J. Am. Chem. Soc. 1934, 56, 495. [Google Scholar] [CrossRef]
  45. Hussain, S.A.; Dey, B.; Bhattacharjee, D.; Mehta, N. Unique supramolecular assembly through Langmuir–Blodgett (LB) technique. Heliyon 2018, 4, e01038. [Google Scholar] [CrossRef] [PubMed]
  46. Ulman, A. Langmuir–Blodgett Films. An Introduction to Ultrathin Organic Films; Academic Press: Cambridge, MA, USA, 1991; 442p. [Google Scholar]
  47. Kim, D.; Kim, S.-H.; Park, J. Floating-on-water Fabrication Method for Thin Polydimethylsiloxane Membranes. Polymers 2019, 11, 1264. [Google Scholar] [CrossRef] [PubMed]
  48. Koschwanez, J.H.; Carlson, R.H.; Meldrum, D.R. Thin PDMS Films Using Long Spin Times or Tert-Butyl Alcohol as a Solvent. PLoS ONE 2009, 4, e4572. [Google Scholar] [CrossRef] [PubMed]
  49. Artificial Cilia for Microfluidics—Sylgard-184 Spin-Coating. Available online: https://willem.engen.nl/uni/intern-mbx/material/Sylgard-184-spincoat.php (accessed on 4 January 2023).
  50. Zhang, W.Y.; Ferguson, G.S.; Tatic-Lucic, S. Elastomer-supported cold welding for room temperature wafer-level bonding. In Proceedings of the 17th IEEE International Conference on Micro Electro Mechanical Systems. Maastricht MEMS 2004 Technical Digest, Maastricht, The Netherlands, 25–29 January 2004; pp. 741–744. [Google Scholar]
  51. Cordura® Fabric. Available online: https://cordura.com/ (accessed on 4 January 2023).
  52. Elastane. Available online: https://sewport.com/fabrics-directory/elastane-fabric (accessed on 4 January 2023).
  53. Gatta. Available online: http://hosieryformen.blogspot.com/2012/06/reviewed-gatta-rosalia-100-denier.html (accessed on 4 January 2023).
  54. Available online: http://polish.xhphapack.com/sale-13146319-tubular-uv-protection-transparent-gpi-40ml-glass-vials.html (accessed on 4 January 2023).
  55. Wiśnik-Sawka, M.; Budzyńska, E.; Puton, J. Application of Ion Mobility Spectrometry for Permeability Studies of Organic Substances through Polymeric Materials. Molecules 2020, 25, 2983. [Google Scholar] [CrossRef] [PubMed]
  56. Wolańska, I.; Piwowarski, K.; Budzyńska, E.; Puton, J. Effect of Humidity on the Mobilities of Small Ions in Ion Mobility Spectrometry. Anal. Chem. 2023, 95, 8505–8511. [Google Scholar] [CrossRef]
  57. Budzyńska, E.; Grabka, M.; Kopyra, J.; Maziejuk, M.; Safaei, Z.; Fliszkiewicz, B.; Wiśnik, M.; Puton, J. Ion mobility spectrometers and electron capture detector—A comparison of detection capabilities. Talanta 2019, 194, 259–265. [Google Scholar] [CrossRef] [PubMed]
  58. David, E.; Tevault Leonard, C.; Buettner Kathy, L. Crouse, VAPOR PRESSURE OF METHYL SALICYLATE AND N-HEXADECANE, Final Report No. ECBC-TR-1184. Available online: https://apps.dtic.mil/sti/pdfs/ADA592343.pdf (accessed on 18 June 2024).
  59. Characteristic Card of DMMP. Available online: https://www.sigmaaldrich.com (accessed on 18 June 2024).
  60. Characteristic Card of DPGM. Available online: https://chemicalsafety.ilo.org/dyn/icsc/showcard.display?p_lang=en&p_card_id=0884 (accessed on 18 June 2024).
  61. Lide, D.R. (Ed.) CRC Handbook of Chemistry and Physics, 85th ed.; CRC Press: Boca Raton, FL, USA, 2004; pp. 6–8. [Google Scholar]
  62. Wiśnik-Sawka, M. Application of Ion Mobility Spectrometer for Organic Substances Diffusion in Polymers. Ph.D. Thesis, Military University of Technology, Warsaw, Poland, 2022. (In Polish). [Google Scholar]
Materials 18 00281 g001
Figure 1. SEM picture of TE-PET supports: (a) 0.2 µm, (b) 1.0 µm; Cordura®: (c) magnification 50×, (d) magnification 200×; and elastane: (e) magnification 100×, (f) magnification; 1000×.
Figure 1. SEM picture of TE-PET supports: (a) 0.2 µm, (b) 1.0 µm; Cordura®: (c) magnification 50×, (d) magnification 200×; and elastane: (e) magnification 100×, (f) magnification; 1000×.
Materials 18 00281 g001
Materials 18 00281 g002
Figure 2. Liquid water permeability testing of the supported PDMS membranes with a red dye betanin water solution. (a) Membranes placed on a sheet of paper; (b) membranes with drops of betanin red dye; (c) sheet of paper after membrane removal for 5 min.
Figure 2. Liquid water permeability testing of the supported PDMS membranes with a red dye betanin water solution. (a) Membranes placed on a sheet of paper; (b) membranes with drops of betanin red dye; (c) sheet of paper after membrane removal for 5 min.
Materials 18 00281 g002
Materials 18 00281 g003
Figure 3. System for measuring membrane self-cleaning.
Figure 3. System for measuring membrane self-cleaning.
Materials 18 00281 g003
Materials 18 00281 g004
Figure 4. Liquid water permeability testing of PDMS membranes cast on four supports: AS—the area of the red spot on the paper; AD—the area of the dye applied to the membrane. Blue color indicates sealed membranes.
Figure 4. Liquid water permeability testing of PDMS membranes cast on four supports: AS—the area of the red spot on the paper; AD—the area of the dye applied to the membrane. Blue color indicates sealed membranes.
Materials 18 00281 g004
Materials 18 00281 g005
Figure 5. Weight loss of water in the glass vials capped with (a) PDMS/elastane membranes with different PDMS thicknesses: x—124 µm; ■—140 µm; +—170 µm; ▲—200 µm; ●—353 µm; ♦—426 µm. (b) PDMS/nylon 15 den membranes with different PDMS thicknesses: ●—0.0 µm; ■—2.7 µm; ♦—4.7 µm; ▲—6.1 µm; +—7.7 µm; x—9.9 µm.
Figure 5. Weight loss of water in the glass vials capped with (a) PDMS/elastane membranes with different PDMS thicknesses: x—124 µm; ■—140 µm; +—170 µm; ▲—200 µm; ●—353 µm; ♦—426 µm. (b) PDMS/nylon 15 den membranes with different PDMS thicknesses: ●—0.0 µm; ■—2.7 µm; ♦—4.7 µm; ▲—6.1 µm; +—7.7 µm; x—9.9 µm.
Materials 18 00281 g005
Materials 18 00281 g006
Figure 6. Water vapour penetration for membranes with different thicknesses: (a) PDMS/elastane membranes; (b) PDMS/nylon 15 den membranes.
Figure 6. Water vapour penetration for membranes with different thicknesses: (a) PDMS/elastane membranes; (b) PDMS/nylon 15 den membranes.
Materials 18 00281 g006
Materials 18 00281 g007
Figure 7. Weight loss of water in the vials capped with doped membranes: (a) PDMS/nylon 8 den; (b) PDMS/nylon 15 den.
Figure 7. Weight loss of water in the vials capped with doped membranes: (a) PDMS/nylon 8 den; (b) PDMS/nylon 15 den.
Materials 18 00281 g007
Materials 18 00281 g008
Figure 8. Water vapour permeability for membranes with different thicknesses: (a) PDMS/nylon 8 den; (b) PDMS/nylon 15 den.
Figure 8. Water vapour permeability for membranes with different thicknesses: (a) PDMS/nylon 8 den; (b) PDMS/nylon 15 den.
Materials 18 00281 g008
Materials 18 00281 g009
Figure 9. Drift time spectra obtained during membrane cleaning: (a) Nyl15; (b) 8PEG600.
Figure 9. Drift time spectra obtained during membrane cleaning: (a) Nyl15; (b) 8PEG600.
Materials 18 00281 g009
Table 1. Admixtures for membrane modification.
Table 1. Admixtures for membrane modification.
AdmixtureMolecular Mass [g/mol]
PEG (Sigma-Aldrich)200 (BioUltra, 200)
400 (BioUltra, 400)
600 (BioUltra, 600)
PPG (P 400, Sigma-Aldrich)400
Calix[6]arene (purity 97%, Sigma-Aldrich).636.7
Table 2. Data for the preparation of different PDMS/support membranes.
Table 2. Data for the preparation of different PDMS/support membranes.
SupportPDMS Concentration
[% w/w]		Pore Diameter
[µm]		PDMS Volume
[mL]		PDMS Membrane Thickness [µm]Abbreviation
TE-PET film100.200T0,2_0
117T0,2_1
0.400T0,4_0
116T0,4_1
215T0,4_2
100T1,0_0
115T1,0_1
424T1,0_4
1.310T1,3_0
214T1,3_2
427T1,3_4
634T1,3_6
Cordura®44(-)00Cord
157Cord1
2110Cord2
441Cord4
1-Cord1T
Elastane25.5(-)3150EL3
4200EL4
5360EL5
Nylon2.915 den0.00Nylon0
0.33.2Nylon0,3
0.54.6Nylon0,5
1.05.7Nylon1,0
1.56.0Nylon1,5
2.07.2Nylon2,0
3.08.6Nylon3,0
Table 3. Data for doped PDMS membranes supported with a fine nylon mesh.
Table 3. Data for doped PDMS membranes supported with a fine nylon mesh.
Membrane CompositionThickness [µm]Molecular Weight of Additives [g/mol]Abbreviation
Open vial0(-)O.V.
Nylon 8 den18(-)Nyl8
Nylon8/PDMS27(-)Nyl8P
Nylon8/PDMS + PEG262008PEG200
Nylon8/PDMS + PEG294008PEG400
Nylon8/PDMS + PEG276008PEG600
Nylon8/PDMS + PPG274008PPG400
Nylon8/PDMS + Calix192648CALIX
Nylon15/PDMS6.1(-)Nyl15
Nylon15/PDMS + PEG3.320015PEG200
Nylon15/PDMS + PEG7.540015PEG400
Nylon15/PDMS + PEG3.760015PEG600
Nylon15/PDMS + PPG3.740015PPG400
Nylon15/PDMS + Calix5.026415CALIX
Table 4. Results of the changes in colorimetric chemical agent detectors after a long period of contact with DPMG, MS, or DMMP in the gas phase. Red (R), green (G), blue (B), hue (H), saturation (S), value (V), and white light components.
Table 4. Results of the changes in colorimetric chemical agent detectors after a long period of contact with DPMG, MS, or DMMP in the gas phase. Red (R), green (G), blue (B), hue (H), saturation (S), value (V), and white light components.
SubstanceExposure Time
[h]		RGBHSVView
MS0544531502475Materials 18 00281 i001
245248513127.552Materials 18 00281 i002
72534543141853Materials 18 00281 i003
240564340112856Materials 18 00281 i004
DMMP0554631502577Materials 18 00281 i005
24504531433650Materials 18 00281 i006
72555130434959Materials 18 00281 i007
240565133454056Materials 18 00281 i008
DPMG0574934532377Materials 18 00281 i009
2454555372355Materials 18 00281 i010
72565547541656Materials 18 00281 i011
240575857100258Materials 18 00281 i012
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content.

Share and Cite

MDPI and ACS Style

Wiśnik-Sawka, M.; Fabianowski, W.; Gajda, D. Innovative Supported Membranes for Ion Mobility Spectrometer (IMS) Sample Introduction Systems with High Permeability Relative to Toxic Agents in Air (TAAs). Materials 2025, 18, 281. https://doi.org/10.3390/ma18020281

AMA Style

Wiśnik-Sawka M, Fabianowski W, Gajda D. Innovative Supported Membranes for Ion Mobility Spectrometer (IMS) Sample Introduction Systems with High Permeability Relative to Toxic Agents in Air (TAAs). Materials. 2025; 18(2):281. https://doi.org/10.3390/ma18020281

Chicago/Turabian Style

Wiśnik-Sawka, Monika, Wojciech Fabianowski, and Dorota Gajda. 2025. "Innovative Supported Membranes for Ion Mobility Spectrometer (IMS) Sample Introduction Systems with High Permeability Relative to Toxic Agents in Air (TAAs)" Materials 18, no. 2: 281. https://doi.org/10.3390/ma18020281

APA Style

Wiśnik-Sawka, M., Fabianowski, W., & Gajda, D. (2025). Innovative Supported Membranes for Ion Mobility Spectrometer (IMS) Sample Introduction Systems with High Permeability Relative to Toxic Agents in Air (TAAs). Materials, 18(2), 281. https://doi.org/10.3390/ma18020281

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop