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1 Note to STRAIVE CE: Please check Section levels

2
3
4 Beyond tTraditional mMethods: Exploring sStrippable gGel bBased oOn dDeep eEutectic
5 sSolvent fFor eEfficient rRadioactive sSurface dDecontamination

6 Sushil M Patil1,2 ,

7 Ruma Gupta1,2 ,*

8 Dibakar Goswami3,2 ,

9 Kavitha Jayachandran1 ,

10 Arkaprava Layek1 ,

11 Prashant Mishra4 ,

12 Suchandra Chatterjee4,2

13 1 Fuel Chemistry Division

14 Bhabha Atomic Research Centre
15 Trombay, Mumbai-400085, India
16 2 Homi Bhabha National Institute
17 Mumbai 400094, India
18 3 Bio Organic Division
19 Bhabha Atomic Research Centre
20 Trombay, Mumbai-400085, India
21 4 Food Technology Division
22 Bhabha Atomic Research Centre
23 Trombay, Mumbai-400085, India
24 4 Homi Bhabha National Institute, Training School Complex
25 Anushakti Nagar, Mumbai 400094, India

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26 * Ruma Gupta, Fuel Chemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai
27 400085, India.
28 Corresponding author email: [email protected]
29 Data S1: Supporting Information.
30 Abstract
31 This study introduces a technique for decontaminating radioactive surfaces by employing a gel,
32 herein termed as rRadiation dDecontamination gGel with eEutectic lLiquids (RADGEL),
33 composed of a deep eutectic solvent and polyvinyl alcohol, with the goal of enabling reuse of the
34 surface post-decontamination. The decontamination effectiveness of RADGEL underwent
35 thorough evaluation through trials conducted on different simulated surfaces, achieving
36 decontamination efficiency up to 99.9% for alpha as well as gamma radionuclides. The various
37 parameters influencing dDecontamination factors such as amount of complexing agent used,
38 polymer film thickness, nature, and magnitude of radioactivity, as well as surface characteristics
39 of substrates to be decontaminated were optimized. Additionally excellent mechanical strength
40 of RADGEL, affirms its potential as practically efficient, cost-effective, and safe option for
41 surface decontamination. The FTIR and scanning electron microscopy (SEM) analysis suggests
42 RADGELs capability for both physical and chemical interactions with contaminants, thus
43 highlighting its comprehensive decontamination efficacy. The outcomes of this study carry
44 substantial implications for the decontamination of surfaces contaminated with various types of
45 radionuclides.
46

47

48

49 Innovative RADGEL, a strippable gel of deep eutectic solvents (DES) and polyvinyl alcohol
50 (PVA), shows remarkable efficiency in surface decontamination against common radionuclides,
51 offering a promising solution to the challenge of nuclear pollution while addressing traditional
52 method drawbacks.

53 Keywords

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54 applications
55 gels
56 separation techniques

57
58

59
60 1. INTRODUCTION
61 Throughout the evolution and utilization of nuclear energy, the persistent threat of nuclear
62 pollution has cast a shadow over humanity. 1, 2 Radioactive contamination, posing a significant
63 hazard to both human health and environmental well-being, arises from the advancement of
64 nuclear energy and radiological incidents. 3–6 Addressing radioactive pollution effectively and
65 facilitating decontamination requires an active exploration of materials and technologies. 7, 8

66 Radioactive contamination, which can manifest in various processes including nuclear accidents,
67 nuclear fuel mining, fuel cycle operations, operation and decommissioning of outdated nuclear
68 facilities, and so forthetc.,9–11 that demands efficient decontamination before any further
69 handling. The International Atomic Energy Agency (IAEA) offers technical reports and
70 guidelines for radiological decontamination during the operation, outage, and decommissioning
71 of such facilities.12–14 The use of surface decontamination technologies, aiming to reduce waste
72 volume while efficiently removing radioactivity, is crucial for cost reduction and enhanced
73 safety during waste treatment and disposal. Various surface decontamination methods
74 namelyviz. chemical, physical, biological, and microbiological approaches, are practiced.15–20
75 Among these, the physical method is commonly employed for swift responses and large-scale
76 decontamination, allowing the rapid removal of radioactive pollutants to help safe disposal.
77 Numerous physical techniques, including mechanical, wet, and dry approaches, are utilized for
78 surface decontamination.21–23 In practice, high-pressure water jet-based washing, a prevalent
79 method primarily used in nuclear accident sites like Chernobyl and Fukushima,24–26 resulted in
80 considerable radioactive wastewater production, while limited contamination removal, making it
81 less favorable.26 Alternatively, techniques such as detergent scrubbing, steam cleaning, vacuums,
82 and the use of strippable coatings are reported in the literature. 23–28 Of late, the use of a strippable
83 coating, which involves using a polymeric solution sprayed to form a strippable film that absorbs
84 and lock surface contamination in solid film. 29–31 Strippable coatings have garnered attention due

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85 to its notable advantages, such as generating only a single solid waste without secondary liquid
86 waste, additional radioactive aerosols, or suspended matter. Numerous experimental studies and
87 applications of commercial products utilizing strippable coatings for radioactive decontamination
88 have been documented, for examples DeconGel, foams, and Argonne super-gel are commercially
89 available, proving effective in surface decontamination during facility operation or
90 decommissioning.23, 27, 28 Although these coatings have been reported to be highly successful in
91 decontaminating surfaces, development of a versatile gel for universal decontamination across
92 various surfaces is still awaited.
93 Recently, deep eutectic solvents (DESs), composed of a quaternary ammonium, phosphonium, or
94 sulphonium salt and a hydrogen bond donor (HBD) with a melting point below 100 °C,32 have
95 been reported to possess good biocompatibility, low production cost, tunability, and good metal
96 oxide solubility, rendering them as potential candidates for economical, efficient, and
97 environmentally friendly decontamination processes. 32–35 Our recent study also demonstrated
98 that, a deep eutectic solvent (DES), developed using heptyltriphenylphosphonium bromide
99 (hydrogen bond acceptor) and decanoic acid (hydrogen bond donor) maintaining a molar
100 composition of 1:2,34, 36, 37 showed promising capabilities in effectively forming complexes with
101 highly toxic radionuclides.36 We envisaged that incorporation of this DES in a strippable gel,
102 may lead to development of an efficient decontaminating agent. Herein, pPolyvinyl alcohol
103 (PVA) has been used as a gel-forming agent due to its superior film- forming ability, easy
104 availability, non-toxicity, and biocompatibility,29, 38, 39 and a gel was developed by combining
105 DES as a complexing agent with effective decontamination properties against common
106 radionuclides like Cs(I) and Pu(IV). The thin film fabricated using developed gel was further
107 characterized to evaluate various physical properties such as tensile strength (TS), elongation
108 break strength (to ensure smooth peeling), and thermal stability. To assess the impact of
109 HBDhydrogen bond donors in deep eutectic solvents (DESs) on film fabrication and
110 decontamination efficiency, various hydrophobic DESs were synthesized, including C7-3LA,
111 C7-2TBABr, and DEHPA-4Betaine. Unfortunately, only the C7-3LA DES yielded a stable and
112 peelable film, achieving successful fabrication at up to 20% DES content. The resulting 20%
113 DES-PVA film exhibited optimal pliability and strength. Subsequent evaluations focused on its
114 decontamination efficiency across common substrates. In contrast to the >99% decontamination
115 efficiency observed for C7-DA DES, the C7-LA film demonstrated relatively lower

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116 decontamination efficiency, ranging from 80%–-90% across all studied substrates. Additionally,
117 the C7-LA film required an extended curing/drying time of 3–-4 days compared withto the
118 10 hours needed for a film of the same thickness based on C7-DA, with relatively lower strength
119 and flexibility. Consequently, C7-DA DES-based films emerge as more favorable, given their
120 shorter fabrication time, excellent decontamination efficiency, and convenient film recovery
121 from surfaces. This study led to the development of a strippable gel named RADGEL,
122 representing “"rRadioactive dDecontamination gGel with eEutectic lLiquids.” RADGEL was
123 evaluated as a potential candidate for surface decontamination applications, through extensive
124 trials on simulated surfaces such as stainless-steel trays, stainless steel fume hoods, PVC floors,
125 granite, glass, and ceramic surfaces.

126 2. EXPERIMENTAL
127 2.1. Materials and mMethods

128 Triphenylphosphine (PPh3 ) (99% purity, CAS number 603-35-0) 1- bBromo heptane (99%
129 purity, CAS Number 629-04-9) dDecanoic acid (DA) (99 % purity, CAS number 334-48-5), and
130 PVAPolyvinyl alcohol (87%–-89% hydrolyzed, CAS Number 9002-89-5) were purchased from
131 Sigma-Aldrich, and used without further purification. All the solutions were prepared in
132 Millipore Milli-Q water (~18 MΏ cm). All solvents (AR grade) used for synthesis were
133 purchased from SRL, India, and were dried according to reported procedures. All the
134 measurements were performed three times, and the average values are presented in the
135 manuscript. The error bars in the reported data represent the standard deviation of the analytical
136 results.

137 .
138 2.2. Synthesis procedure of DES

139 A DES, based on heptyltriphenylphosphonium bromide ([Heptyltriphenylphosphonium bromide

140 which act as hydrogen bond donor is synthesized by refluxing tTriphenylphosphine [(PPh3 ])
141 and n-bBromo heptane in dry acetonitrile according to reported procedure, as before.34, 36, 37 )] and
142 decanoic acid (DA, Sigma- 94 Aldrich, 99%), was prepared following a procedure reported
143 previously by our group34, 36, 37 and was characterized using FT-IR, NMR, thermogravimetric
144 analysis (TGA), and differential scanning calorimetry (DSC).34

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145 2.3. Synthesis of RADGEL

146 10% polyvinyl alcohol (PVA) in Milli- Q water was heated at 70°°C with stirring for 2 h untill
147 complete dissolution of PVA. Next, the solution was enriched with DES at different proportions
148 (5%–-20% w/w), and the stirring was continued until a unified, adhesive gel-forming solution
149 was obtained. It is worth noting that, in contrast to other gels outlined in existing literature, 29, 30,

150 40–42 the incorporation of a plasticizing agent is preventable, as the DES itself serves as both a
151 plasticizer and a complexing agent. The resultant gel solution displayed a white color.

152

153 2.4. Physicochemical characteristics of the film created using gGel

154 To assess the ability of the gel to form a film on various surfaces, thin films were created from
155 the synthesized gel through a casting process on three distinct surfaces: a polystyrene tray, a
156 silicon mold, and glass. This evaluation is crucial for addressing radioactive contamination on a
157 range of surface types.

158 2.5. Influence of polymer coating thickness on decontamination factor

159 Approximately 1 mL of radioactive Pu239 (96.6 Bqcm−-2 ) were applied to six circular (diameter
160 10 cm2 ) glass and PVC plates, allowed to dry, and then various amounts of RADGEL were used
161 to cover the contaminated region which is equivalent to different thicknesses measured in
162 microns. The thickness of the polymeric gel has been calculated via Equation 1.
163 Thickness = Volume (V)/ π r2 (1)
164 2.6. Influence of contamination level on decontamination factor

165 Varying amount of a Pu239 radioactive solution, with an estimated activity level (430–-
166 3360Bqcm−-2 ), were applied to the surface of five circular (10 cm2 ) glass and PVC plates,
167 allowed to dry at room temperature, and then were covered with 1 mL of RADGEL. After
168 curing, the polymer coating was peeled off. The contamination monitor was used to measure the
169 contamination levels before and after decontamination.
170 2.7. Decontamination protocol

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171 Solution of radioisotopes 137 Cs and 238 Pu with known activities were spread on different types of
172 surfaces such as (glass, PVC, aAsbestos sheet, sStainless steel surface) with known cross-
173 sectional area and then dried out. The contamination level in Bq/cm2 was measured immediately
174 after the solution dried. The contaminated regions were covered with RADGEL, dried for 24 h,
175 and the dried film was peeled out. The final contamination level was measured in Bq/cm2 . The
176 decontamination efficiency (%DE) was computed using Equation (2).
177 %DE = ([[(Ci−–Cf])/Ci)] × *100 (2)28
178 wWhere, Ci is the surface contamination level in Bq/cm2 before decontamination and Cf is the
179 surface contamination level in Bq/cm2 after decontamination.

180 The decontamination factor (D.F.) for each coating layer was also calculated using Equation (3).
181 D.F. = Ci /Cf (3)28
182 Scheme 1 outlines the protocol adhered to during the RADGEL investigation for decontamina ting
183 surfaces contaminated with 239 Pu and 137 Cs. In summary, the proposed decontamination protocol
184 involves:

185 1. Spilling of radioactivity onto the surface, leading to a specific level of contamination.

186 2. Applying RADGEL to the contaminated surface and allowing it to dry for 24 hours

187 3. Peeling off the film from the surface.

188 4. Measurement of surface contamination, and calculation of decontamination parameters.

189
190 SCHEMEcheme 1. Series of decontamination procedures used for surface cleansing utilizing
191 RADGEL.
192
193
194 3. RESULTS AND DISCUSSIONS
195 3.1. Synthesis and cCharacterization of DESs
196 Based on our previous studies with the DES composed of n-hHeptyltriphenylphosphonium
197 bromide and dDecanoic acid, capable of forming complexes with highly toxic radionuclides,34, 36,

198 37 we developed a gel incorporating poly vinyl alcohol (PVA) and varying concentrations of the
199 DES (5%–-20%, w/w) with the intention of utilizing it as a decontamination agent for
200 radioactive surfaces. The amount of DES in the gel was limited to 20% (w/w), since higher DES

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201 loading restricted the uniform gel formation. AlsoIn addition, the % loading of the DES, as a
202 complexing agent in the gel, is much more than similar decontaminating gels where complexing
203 agents like EDTA, DTPA, catechol and so forthetc. have been used in presence of a plasticizer.43,
204 44 . This presents an inherent benefit, as the ability to incorporate a greater amount of complexing
205 agent into the gel without sacrificing its physical properties could result in a higher
206 decontamination factor.

207 FigureIGURE 1 shows that the decontamination factor (DF) displayed an ascending pattern with
208 increasing DES content, with a maximum DF obtained with a gel containing 20% DES. The
209 corresponding values are presented in Table S1. Moreover, it was observed that PVA films without
210 DES or with low DES content were prone to breakage when being removed from surfaces might
211 be due to their limited elasticity. Nevertheless, film flexibility improved with increasing DES
212 content, and, among the prepared gels, the flexibility was maximum for the film composed of 20%
213 DES and 80% aqueous PVA. Consequently, the 20% PVA-DES gel (RADGEL) was selected for
214 further decontamination studies owing to its exceptional decontamination potential, high elasticity,
215 and easy peel ability.
216

217 FIGURE 1. Decontamination factor with increasing percentage of deep eutectic solvents (DES)
218 in radiation decontamination gel with eutectic liquidsRADGEL.
219 The PVA-DES film (20%DES) fabricated was characterized by FTIR spectroscopy. As can be
220 seen from Figure 2 the film exhibited all the characteristic peaks corresponding to DES as well
221 as PVA confirming absence of any chemical modifications or cross- linking driven by DES.

222

223 FIGURE 2. The FTIR spectra of radiation decontamination gel with eutectic liquids (RADGEL)
224 (20% deep eutectic solvent [DES]) film vis-à-vis polyvinyl alcohol (PVA) film and DES.
225 To gain a deeper insight into the interaction and bonding between PVA and DES, the RADGEL
226 (20%) film was sonicated in acetone for 2 hours, followed by subsequent air- drying. Figure
227 3a,baA-bB illustrates a comparison between the FTIR spectra of the PVA-DES film before and
228 after acetone washing, in contrast to the spectra of solely the PVA film, with no inclusion of
229 DES. Notable differences were evident in the film after acetone washing, where the intensity of
230 the carbonyl stretching peak significantly decreased, resembling those of only PVA film, with
231 overlapping peak positions. Intriguingly, peaks associated with DES at 690 cm−-1 , 722 cm−-1 ,
232 895 cm−-1 , 995 cm−-1 , and 1588 cm−-1 completely disappeared after acetone washing. This
233 suggested the complete removal of DES from the film after acetone washing, as DES is soluble

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234 in acetone, leaving only PVA behind. Conversely, DES recovered from the extracted acetone
235 solution displayed overlapping peak positions with pure DES, as depicted in the FTIR spectra in
236 Figure 3ccC. Based on these observations, we deduce that the interaction between DES and PVA
237 involved weak bonding, and there was no involvement of cross-linking in the structure.
238
239
240
241 FIGURE 3. FTIR spectra of polyvinyl alcohol (PVA) film vis-à-vis radiation decontamination
242 gel with eutectic liquids (RADGEL) (20%) film before and after acetone washing in the range
243 (aA) 700– cm−-1 -1800 cm−-1 , and (bB) 1600– cm−-1 -1800 cm−-1 . (cC) FTIR spectra of freshly
244 prepared deep eutectic solvent (DES) vis-à-vis DES recovered from acetone washing of the film.

245 The effectiveness of surface decontamination is primarily influenced by various factors,

246 including the proportion of the complexing agent in the gel composition, the volume (thickness)
247 of the gel layer, and the extent of contamination present on the surface. This study has
248 specifically investigated these variables to demonstrate the efficacy of the formulated polymeric
249 gel in decontaminating surfaces contaminated with 137 Cs and 238 Pu. The surfaces under
250 consideration include glass, PVC flooring, plastic, asbestos sheet, and stainless steel (SS).

251

252

253 3.2. Mechanical properties of film

254 The tensile strength (TS) and the elongation at break (EB) are two important mechanical
255 properties of a strippable film that can predict the suitability of using RADGEL as a peel-off
256 decontaminating gel. Since these mechanical properties depend on the casting material, we
257 measured both the TS and the EB on different casting materials namelyviz. silicon mold,
258 polystyrene, and glass. The mechanical properties of films are given in Table 1. The tensile
259 strength (TS) was in the range of 5.4–-8.2 MPa. Previously, TS of PVA films, obtained with
260 different compositions of plasticizers, were reported on glass surface (3.5 MPa),(Sudhamani et
261 al., 2003).45 , on silicon mold (10 MPa), (Limpan et al., 2010).46 , and on polystyrene dish (44
262 and 39 MPa).(Sonker et al., 2016)47,48 and Boonsak et al (2019) .Thus, the TS wasere affected by
263 the nature of the plasticizers. The % EB was found to be in the range of 64.9%–-139.6% and
264 varied on type of casting material similar to TS (Table 1). Likewise, this property was also

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265 dependent on the plasticizer material used in formation of the film, as the reported %EB values
266 for PVA films with different plasticizers on different surfaces varied from 112, (Sonker et al
267 (2016)47 , 240, (Sudhamani et al., 2003)45 and 250 (Limpan et al., 2010).46 The obtained films
268 were in the range of moderate TS and high % EB, which will be useful in easy peel -off of these
269 films from different contaminated surface after drying.

270 3.3. Color properties of films

271 The colors of the films obtained are given in Table 1. The highest lightness (L*) value was found
272 the film casted on silicon mold whereas film casted on glass surface and polystyrene films had
273 similar L*. This indicated that the film, which was casted on silicon mold had highest whiteness
274 as compared withto other films. The a* and b* values were highest in film casted on silicon mold
275 followed by film casted on glass plate and lowest in film casted on polystyrene. This showed that
276 film casted on silicon mold had higher component of redness and yellowness as compared withto
277 other films, whereas film casted on polystyrene had lowest. The opacity of films was also in
278 same order of a* and b* values showing that most transparent film was the one casted on
279 polystyrene and least transparent film was the one casted on silicon mold.

280

281 TABLE 1. Mechanical, cColor, tThermal, and moisture properties of different films.
RADGEL- cCasting material
Film pProperty Parameter Silicon mMold Polystyrene Glass
Mechanical Tensile strength (TS) 7.83 ± 1.05 8.29 ± 0.37 5.45 ± 0.82
(MPa)

Elongation at break 64.93 ± 10.26 107.96 ± 15.92 139.60 ± 20.63

(%EB)

ColorColour L* (Lightness) 53.04 ± 5.42 43.55 ± 0.78 43.56 ± 0.54

a* (+rRed to −– 0.24 ± 0.08 − 0.08 ± 0.01 0.02 ± 0.01

gGreen)

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b* (+yYellow 0.59 ± 0.07 − 0.23 ± 0.07 0.14 ± 0.08

to −− bBlue)

Opacity (%) 18.87 ± 1.37 10.23 ± 1.28 14.77 ± 0.20

Thermal Melting temperature. 288.33 ± 2.52 288 ± 2 287.67 ± 3.51

(°C)

Degradation 327.77 ± 0.68 327.66 ± 1.53 328 ± 1.1

tTemperature. (°C)

Moisture Water sSolubility (%) 48.99 ± 5.31 32.24 ± 5.42 23.56 ± 2.36
sSensitivity

Water vVaporVapour 3.09 ± 0.67 4.26 ± 0.03 5.06 ± 0.31

pPermeability

(10−-8 g mm h−-
1 cm−-2 Pa−-1 )

282 Abbreviations: EB, elongation at break; RADGEL, radiation decontamination gel with eutectic
283 liquids.

284 3.3.1. DSC of films

285 The thermal properties of different films were given in Table 1. There were no changes in
286 thermal properties of films and all films had melting temperature (Tm) around 288 °C. The
287 temperature at which the polymer degraded completely was around 328 °C. This film is resistant
288 to high temperatures, hence useful in removing contaminants even at high temperatures. Films
289 using PVA as a gel-forming material are also known to withstand high temperatures.45, 49

290 Previously, high Tm for PVA films have been reported, 202 °C, (Sudhamani et al., 2003)45 , 225
291 °C, (Kashyap et al., 2016)49 and 220 °C. (Tsukada et al., 1992)50 .

292

293 3.3.2. Water solubility and water vapor permeability of films

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294 The water solubility and water vapor permeability (WVP) of films are crucial attributes, as
295 increased moisture absorption from the atmosphere can result in challenges in detaching the film
296 from the surface, caused by swelling and subsequent weakened strength. Table 1 illustrates the
297 water solubility and WVP of the films. Films cast on various surfaces were immersed in water
298 for 15 minutes with sonication to achieve a cloudy dispersion. The water solubility of the films
299 ranged from 23.6% to 48.9%.Previous reports for films obtained using PVA as a gel forming
300 material showed the water solubility in the range of 23.6%– ̶ 100% depending on the degree of
301 hydrolysis and molecular weight of PVA films. 51 The WVPwater vapor permeability of films
302 was in the range of 3.1– -5.1 ×x 10−-8 g mm h−-1 cm−-2 Pa−-1 . There was minimal effect of
303 casting material on WVPwater vapor permeability of films. Previous reports showed that
304 WVPwater vapor permeability of films using PVA and different plasticizers, is dependent on
305 degree of hydrolysis and molecular weight. 51, 52 Different PVA films with partial hydrolysis and
306 low molecular weight showed lower water solubility and WVP as compared withto fully
307 hydrolyzed and high molecular weight PVA films.51

308 The surface characteristics of DES-PVA films, including specific surface area and pore volume
309 at different film thicknesses, were investigated using Brunauer–Emmett–Teller (BET) isothermal
310 analysis with N 2 at 77 K. Examination of the N 2 adsorption/desorption isotherm curves in Figure
311 4 indicated that all films, regardless of thickness, exhibited a small hysteresis loop in the high-
312 pressure region, confirming the meso-porous nature of the surface. The specific surface area of
313 the films gradually decreased with increasing thickness, measuring 67 m2 /g, 31 m2 /g, and
314 23 m2 /g for film thicknesses of 0.105 mm, 0.21 mm, and 0.305 mm, respectively.
315 Additionally, the pore distribution indicates a relatively uniform pattern, providing a large
316 accessible surface area for accommodating radioactive contaminants and thereby contributing to
317 excellent decontamination efficiency.

318

319

320 FIGURE 4: Comparison of Brunauer–Emmett–TellerBET aAdsorption/dDesorption isotherm for

321 PVA-DES film with different thickness. DES, deep eutectic solvents; PVA, polyvinyl alcohol.
322 3.4. Decontamination studies using RADGEL

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323 Initially, the volume of RADGEL required for decontamination purpose was optimized by
324 using different amounts of gel (0.2–-1.5 mL) on a 239 Pu contaminated PVC surface. Based on
325 Table 2 and Figure 5, the decontamination factor for 239 Pu exhibited significant variation
326 between the small and high volumes of RADGEL. Specifically, the gel with a volume of 1 mL
327 (equivalent to a thickness of 1.05 mm) achieved the highest decontamination factor, reaching
328 459, corresponding to %DE value of 99.78. As the polymeric-gel volume increased beyond this
329 point, there was a noticeable decrease in both the decontamination factor and %DE. This
330 outcome can be attributed to the formation of a thick layer of gel when the RADGEL volume
331 exceeded 1 mL, hindering the complete drying of all gel quantities within the optimal contact
332 time. Consequently, this inhibited effective interaction with the radioactive material distributed
333 on the surface.28
334 TABLE 2: Measured DF and %DE values for different volumes of RADGEL for
335 decontamination of PVC surface.
Contamination
RADGEL Thickness level (Bqcm−-2 )
volume of film (239 Pu) Decontamination Decontamination
(mL) (mm) Surface Initial Final efficiency (DE%) factor (DF)
0.25 0.26 PVC 96.64 2.24 97.67 43 ± 3.9
0.5 0.52 96.64 2.63 97.21 36 ± 4.2
0.75 0.78 96.64 1.82 98.11 52 ± 3.8
1 1.05 96.64 0.21 99.78 459 ± 12.0
1.5 1.57 96.64 1.24 98.71 77 ± 6.1
336 Abbreviation: RADGEL, radiation decontamination gel with eutectic liquids.
337
338
339
340
341 FIGURE 5. The variation of decontamination factor as function of radiation decontamination gel
342 with eutectic liquidsRADGEL volume.
343
344
345

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346 FIGURE 6. The variation of decontamination factor as a function of (aA) concentration239 Pu

347 aActivity and (bB) nNature of contaminated surfaces (aAlpha active).
348
349 Next, the decontamination efficiency of 1 mL RADGEL towards decontaminating varied
350 activity levels on PVC surface was studied. Figure 6aaA indicated that the decontamination
351 factor exhibited an initial rise with the escalation of 239 Pu contamination levels, reaching a peak
352 at 2200 Bq/cm2 , and subsequently declined on the PVC surface. This could be explained by the
353 saturation of the available complexing sites in RADGEL compared withto the moles of
354 radioactive material available for complexation. 23, 53–55 Next, decontamination efficiency of
355 RADGEL in different contaminated surfaces (gGlass sStainless steel, PVC, and pPlastic), were
356 studied using the optimized volume of RADGEL (Figure 6bbB). In all the cases, the %DE was
357 found to be very high in the range of 99.5%–-99.9%. The tables corresponding to values of
358 Figure 6a,baA and 6bB are presented in Table S2 and S3. (S.I). Further RADGEL exhibits
359 excellent decontamination efficiency for gamma active radionuclides as shown in Figure 7.
360

361 FIGURE 7. The variation of decontamination factor as a function of nNature of contaminated

362 surfaces (gGamma active).
363
364 From Figure S1 (ESI), it is confirmed that the decontamination efficiency of RADGEL was
365 consistent, effective, and reliable across various substrates, including glass, PVC flooring, and
366 aluminum. Notably, the presence of different radioactive contaminants such as 137 Cs and 239 Pu

367 did not significantly impactaffect the overall efficiency of RADGEL in removing and mitigating
368 contamination. This robust and uniform decontamination effectiveness across diverse substrates
369 and radioactive contaminants underscores the versatility and reliability of RADGEL as a
370 promising decontamination agent for various surfaces and radioactive species.
371

372
373
374
375
376
377

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378
379 FIGURE 8. FTIR comparison of (aA) PVA-DES film with and without uUranyl nitrate (bB)
380 aAcetone washed PVA-DES-UO2 film to that of PVA-DES UO 2 , PVA-DES, and only PVA film
381 (cC) DES to that one recovered from acetone after washing. DES, deep eutectic solvents; PVA,
382 polyvinyl alcohol; RADGEL, radiation decontamination gel with eutectic liquids.
383

384 3.5. Mechanism of decontamination

385 To gain insight into the decontamination process, we utilized natural uranium in the form of
386 uranyl nitrate as a contaminant. The affected surface underwent treatment with RADGEL under
387 optimized conditions. Upon comparing the FTIR spectra of the recovered films after
388 decontamination with films retrieved from uncontaminated surfaces lacking any radioactive
389 contaminants (Figure 8aaA), a notable U〓O stretching peak at 921 cm−-1 was identified,
390 confirming the binding of the uranyl ion to the film (see inset Figure 8aA). Following this, the
391 uranyl-contaminated film was subjected to multiple washings with of acetone (5 × 5 mlL). The
392 acetone-washed film was then compared with films formed from RADGEL, both with and
393 without uranyl, as well as a bare PVA film, using FTIR spectra. Remarkably, the uranyl peak at
394 921 cm−-1 was entirely eradicated after washing (see Figure 8bbB). Conversely, the DES,
395 recovered from acetone after concentrating under vacuum, displayed a distinct uranyl signature
396 at 921 cm−-1 (see Figure 8ccC).37 These observations indicate that the metal ion's sorption may
397 be governed by a chemisorptions process, implying the formation of a complex between the DES
398 and the metal ion of interest. This is consistent with our prior studies, where the DES exhibited
399 robust complexation with U and Pu.36 Another possibility is that the metal ion adheres to the
400 surface or permeates the specimen through small capillaries. The physical/chemical
401 characteristics and radius of various metal ions, as well as the porosity and size of capillaries,
402 will decide the adhesion and diffusion capabilities, suggesting the physical sorption of the metal
403 ions.28 Consequently, the decontamination process with RADGEL likely encompasses a
404 combination of both physical and chemical mechanisms.

405 The scanning electron microscopy (SEM) images of the developed decontamination film crafted
406 for the decontamination of radioactive surfaces vividly reveals the intricate material structure,
407 displaying a distinctive network of uniformly distributed pores (Figure 9aaA). These pores play a
408 pivotal role in enhancing the film's decontamination effectiveness. The high-resolution image

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409 captures the interconnected network of pores, showcasing their diverse sizes. This porous
410 architecture significantly augments the film's specific surface area, facilitating both physical and
411 chemical adsorption for the efficient decontamination of radioactive contaminants. In Figure
412 9bbB, the SEM image depicts the post-treatment transformation of the decontamination film on a
413 radioactive surface with uranyl activity. This transformation is characterized by the presence of
414 blocked pores and an altered morphology, signifying the film's successful removal and
415 containment of radioactive contaminants. The blocked pores visually confirm the film's
416 capability for both physical and chemical interactions with contaminants, highlighting its
417 comprehensive decontamination efficacy. Figure 9ccC illustrates the SEM image of the PVA
418 film without the addition of DES, revealing a dense and continuous structure, devoid of
419 discernible pores (Figure 9aaA). In contrast, Figure 9ddD shows the SEM image of the
420 decontamination film post-treatment on a radioactive surface, followeding by washing and
421 sonication with acetone. This image showcases open pores, indicating a successful
422 decontamination process and the removal of DES and radioactive contaminants. The SEM
423 analysis underscores the physical changes in the film's microarchitecture and signifies the
424 systematic and efficient removal and recovery of contaminants during the decontamination
425 procedure. Figure 10 presents EDXRF comparison of RADGEL film post UO 2 decontamination
426 vis-à-vis the same film after acetone washing. The uranium peak observed at 13.4 KeV before
427 acetone wash, was completely vanished after acetone washing, which is in corroboration with
428 conclusions derived from FTIR and SEM analysis.

429

430 FIGURE 9. Scanning electron microscopy (SEM) images (aA) PVA-DES (80:20) film, (bB)
431 pPost-decontamination of PVA-DES (80:20) film with uranium activity, (cC) oOnly PVA film
432 without the addition of C7-DES and (dD) )tThe change of film in fFigure B after thorough
433 washing in acetone. DES, deep eutectic solvents; PVA, polyvinyl alcohol.
434

435

436

437

438

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439 FIGURE 10: Comparison of PVA-DES-U film using EDXRF before and after undergoing
440 acetone washing. DES, deep eutectic solvents; PVA, polyvinyl alcohol.
441
442 There are several kinds of polymer coatings for surface radioactivity decontamination reported in
443 literature. Table 3 shows comparison of decontamination performance of few PVA based gel
444 coating for 137 Cs over Glass surface as well as commercially available DeconGel for comparable
445 137 Cs activity levels. It was evident that RADGEL has highest DF of 514, even higher than
446 commercially available DeconGel. Further, Table 4 clearly demonstrates the higher
447 decontamination efficiency of RADGEL in decontaminating 239 Pu-active steel surface compared
448 withto that of DeconGel.

449

450 TABLE 3: Assessment of RADGEL's effectiveness in decontaminating 137 Cs compared withto

451 PVA based formulations found in literature, which utilize various complexing agents, as well as
452 commercially available DeconGel.
Decontamination Decontamination eEfficiency
Material factor (DF) (%DE) Reference
PVA-gel 6.6 85 Experimental

PVA-EDTA 111.4 99.1 56

PVA-oOxalic acid 230 99.6 56

PVA-bBorax- 16.8 94.3 57

bBeantonite

DeconGel 315 99.7 28

PVA-C7DES 514 99.8 Present work

453 Abbreviations: DES, deep eutectic solvents; PVA, polyvinyl alcohol; RADGEL, radiation
454 decontamination gel with eutectic liquids.

455 TABLE 4: Evaluating RADGEL's effectiveness in decontaminating 239 Pu in comparison withto

456 the commercially available DeconGel.
Decontamination eEfficiency (DE%)
Material (sSteel surface) (iIn single coating) Reference

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DeconGel 57 58

PVA-DES 99.7 Present work

457 Abbreviations: DES, deep eutectic solvents; PVA, polyvinyl alcohol; RADGEL, radiation
458 decontamination gel with eutectic liquids.

459

460 4. CONCLUSIONS
461 In addressing the ongoing challenge of nuclear pollution, this study introduces RADGEL, an
462 innovative strippable gel comprised of deep eutectic solvents (DESs) and polyvinyl alcohol
463 (PVA). Focused on surface decontamination, the research targets drawbacks of traditional
464 methods and underscores RADGEL's efficacy against common radionuclides, achieving
465 decontamination efficiency ranging from 97% to 99%. Factors influencing decontamination
466 include the agent used, polymer film thickness, radioactivity, and surface characteristics. Careful
467 material selection and extensive trials affirm RADGEL's potential as a practical and
468 environmentally friendly solution. The incorporation of DES not only enhances decontamination
469 but also holds promise for reducing waste, signifying a noteworthy advance in nuclear pollution
470 management. RADGEL emerges as a cost-effective and safe option for surface decontamination
471 during facility operation or decommissioning, contributing to sustainable practices in nuclear
472 energy. Moreover, the generation of secondary wastes from the decontamination process in solid,
473 small, compressible, and combustible forms enhances the efficiency and economy of radioactive
474 waste management compared withto alternative decontamination techniques.

475 DATA AVAILABILITY STATEMENT

476 The data that support the findings of this study are available from the corresponding author upon
477 reasonable request.

478
479

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