Skip to main content
Heritage Science
Download PDF
Download ePub

Enhancement of the hygrothermal ageing properties of gelatine films by ethylene glycol diglycidyl ether

Heritage Science volume 12, Article number: 297 (2024) Cite this article

Abstract

Owing to the instability of gelatine in hygrothermal environments, gelatine-based cultural heritage undergo various deterioration processes, such as cracking, peeling, warping, curling and fracture, posing significant threats to its long-term preservation. Building on previous research, this study investigates the stability of polyol glycidyl ether–gelatine composite films under high-humidity and high-temperature conditions using ethylene glycol diglycidyl ether (EGDE) as a model compound. The hygrothermal ageing properties of EGDE–gelatine composite films are evaluated in terms of macrosize, mesoscopic structure, surface properties and mechanical properties. Results indicate that EGDE enhances the dimensional stability and swelling ratios of the composite films, stabilizes the pore structure and distribution and maintains the hydrophilicity and molecular structural stability under hygrothermal ageing conditions. Furthermore, the incorporation of EGDE leads to superior stress–strain properties of the composite films in such challenging environments. This study provides valuable experimental data for the preparation and conservation applications of gelatine-based cultural heritage materials.

Introduction

Gelatine, a natural polymer derived from animal protein, has been historically utilised as a sizing material when producing cultural heritage items such as ancient calligraphy items and paintings [1, 2]. In contemporary settings, the emergence of the photographic technology has accelerated the development of photosensitive emulsions. As a primary film-forming substance used in photosensitive emulsions, gelatine is extensively employed in photographic archives, including photographs, films and glass negatives [3,4,5]. Previous studies have indicated that unstable dry–wet cycling conditions can cause protein molecule aggregation in the gelatine emulsion film, leading to shrinkage and deformation, ultimately leading to embrittlement, shedding, curling and fracture of the emulsion layer in gelatine-based photographic archives [6, 7]. Our recent observations indicated that the combined effect of heat and humidity further exacerbates the shrinkage deformation of gelatine films. Therefore, developing a simple method to enhance the stability of gelatine films in high-humidity and high-temperature environments is crucial for preserving of such cultural heritage.

Conventionally, aldehyde crosslinking agents are employed to modify gelatine gels and films [8,9,10,11,12,13,14]. However, toxicity associated with aldehydes raises safety concerns when used in applications involving human contact. Recent in vitro studies have shown that the cytotoxicity levels of epoxy compounds are within acceptable limits [15], leading to their adoption in pharmaceutical and biomaterial applications [16,17,18]. Among the multi-functional epoxy crosslinking agents, water-soluble polyol glycidyl ethers offer a promising yet underexplored alternative to crosslinking polymers containing hydroxyl, amine and carboxyl groups [19]. These agents are also used in surface modifications to bind hydroxyl groups with proteins and in membrane technologies [20,21,22]. For instance, 1,4-butanediol diglycidyl ether has been used to chemically crosslink gelatine with chondroitin and hyaluronic acid, considerably influencing the physical and biochemical properties of the resulting hydrogels based on the degree of chemical crosslinking and position of reaction substitution [23,24,25]. Ethylene glycol diglycidyl ether (EGDE) has been incorporated into adhesive systems as a viscosity-reducing agent, plasticiser and crosslinking agent, enhancing the performance of soybean-based adhesives [26]. Polyethylene glycol diglycidyl ether has been used to crosslink and modify silk fibroin proteins and alginates, improving their biological properties, hydrophobicity and solubility through chemical functional group modifications [27]. Recently, our research group employed glycerol triglycidyl ether (GTE) as crosslinking agent and plasticiser in photographic gelatine films, examining variations in hygroscopicity, swelling and flexibility after the modification [28]. The chemical structures of EGDE and GTE molecules have typical ethylene oxide end groups, presenting high reactivity, which can crosslink with the amino groups in gelatine molecules through a ring-opening reaction to form C–O–C bonds [29]. Polyols are commonly used as plasticizers to regulate the flexibility and water-holding properties of gelatine films in food and biomedical applications [30, 31], such as glycerol, propylene glycol, diethylene glycol, and ethylene glycol, which can be inserted into the gelatine films to form a hydrogen bonding network [32,33,34,35,36,37]. Therefore, previous studies have primarily focused on the physical and chemical modifications of gelatine, polysaccharides and other biological materials using polyol glycidyl ether (for example, GTE, EGDE, etc.) as a crosslinking agent or plasticiser.

However, reports on the ageing resistance and longevity of modified films remain scarce. Notably, elucidating the anti-ageing properties of modified gelatine films under extreme conditions is crucial for guiding the stable preservation of gelatine-based cultural heritage. To address this gap, we used EGDE as a representative compound to investigate the stability of polyol glycidyl ether–gelatine composite films under severe hygrothermal conditions (RH = 85% and T = 60 °C). The hygrothermal ageing performance of the films was extensively evaluated, considering aspects such as macrosize, mesoscopic structure, surface properties and mechanical properties. The research methodology is depicted in Fig. 1. This study explored the dimensional changes, swelling properties, surface morphologies and pore structures of the EGDE–gelatine composite films before and after hygrothermal ageing. The effect of varying the EGDE concentrations on the macroscopic and mesoscopic stabilities of the EGDE–gelatine composite films under these conditions was also assessed. In addition, the study analysed changes in surface hydrophobicity, crystallinity, molecular functional groups and stress–strain properties to understand the effects of hygrothermal ageing on the films at different EGDE concentrations. The findings offer valuable experimental data and theoretical insights for the restoration and protection of fragile gelatine-based cultural heritage.

Fig. 1
figure 1

Research idea and experimental design of this study

Full size image

Experimental section

Sample preparation

An appropriate amount of gelatine powder (photographic grade, Aladdin Chemical Reagents Ltd.) was weighed and immersed in distilled water. After it was completely dissolved, it was heated at 60 °C for 50 min with stirring to produce a transparent homogeneous solution with a 5 wt% concentration. Then, an appropriate amount of EGDE (biological grade, Aladdin Chemical Reagent Co., Ltd.) was added to the above transparent solution to make a mixture, and stirring was continued at 60 °C for 90 min to prepare EGDE-gelatine solutions with concentrations of 0 wt% (control), 0.5 wt%, 1 wt%, 1.5 wt% and 2 wt%, respectively. The above mixtures were transferred to petri dishes using the flow-through film-forming method and dried naturally at room temperature to form a film.

Characterisation methods

  1. (1)

    Hygrothermal ageing conditions: the relative humidity (RH) of hygrothermal ageing was 85%, the temperature (T) was 60 °C, and the ageing time was 144 h. In order to investigate the physicochemical stability of the EGDE–gelatine composite films by hygrothermal ageing, the prepared control film and composite films with different EGDE concentrations were subjected to hygrothermal ageing experiments in a test chamber.

  2. (2)

    Dissolvability test: all the composite films before and after ageing were dried in a blower oven at 60 °C for 48 h, and these samples were weighted to obtain W1. Afterwards, they were immersed into a container with deionized water and fully dissolved for 8 min, and then the films were taken out of the container, wiped with a filter paper to remove the excess water on the surface, and these films were weighed to obtain W2. The weight swelling ratio was calculated with Eq. (1).

    $${\text{Weight}}\;{\text{swelling}}\;{\text{ratio}}\;\left( \% \right) = \left( {{\text{W}}_{{2}} - {\text{W}}_{{1}} } \right)/{\text{W}}_{{1}} \times {1}00\% .$$
    (1)
  3. (3)

    Scanning electron microscopy (SEM) test: to investigate the effect of hygrothermal ageing on the pore structure of the composite films, the dissolved composite films were freeze-dried, and then they were attached on an aluminium sample stage with conductive adhesive. The samples surface was sprayed with gold for 80 s using an ion sputtering device (SCD005, Baltek, Liechtenstein, Germany), and the surface morphologies and the sample structures were observed by scanning electron microscopy (SEM, TM3030, Hitachi, Japan).

  4. (4)

    Low-field nuclear magnetic resonance (NMR) test: to further investigate the effect of hygrothermal ageing on the pore sizes and distributions of these composite films, the prepared gelatine film samples with different shrinkage rates were swollen in distilled water, and then the T2 inversion spectra of gelatine films with different shrinkage rates were tested by a NMR analyzer (MicroMR12–025 V). Low-field NMR is used to infer porosity, pore size distribution, and other information related to pore structure by measuring the intensity and characteristic parameters of the NMR signal.

  5. (5)

    Contact angle test: the contact angle of gelatine film’s surface was investigated. The OCA20 static video contact angle meter (Dataphysics, Stuttgart, Germany) was used to detect the contact angle changes of the composite films before and after hygrothermal ageing.

  6. (6)

    X-ray diffraction test: the crystal structures of the composite films were analysed using X-ray diffraction (XRD; Smart Lab, Rigaku Corporation, Japan) using a voltage of 45 kV, current of 200 mA, scan speed of 5°/min, and 2θ scan range of 2–50°.

  7. (7)

    Fourier transform infrared (FTIR) spectroscopy test: the gelatine films were tested at room temperature and ambient humidity using a FTIR PerkinElmer Spectrum 2 (Vertex 70, Bruker, Karlsruhe, Germany) with total reflection mode. The wavenumber range was between 500 and 4000 cm−1 with a resolution of 4 cm−1, and the scan number was 32 times. In order to reduce the influence of carbon dioxide and water vapor on the infrared spectrum, the infrared spectrum of the sample was deducted from the background contribution.

  8. (8)

    Stress–strain test: the mechanical properties of these films were tested with a speed of 5 mm/min at room temperature using a universal material testing machine with PT-1176PC computerized servo-system (Dongguan Baoda Instrument Co., Ltd., China), and then the stress–strain curves before and after hygrothermal ageing were recorded for the EGDE–gelatine composite films.

Results and discussion

Macrosize and swelling properties

To study the anti-ageing properties of gelatine films as influenced by EGDE, we monitored changes in the size of the composite films with varying EGDE concentrations before and after ageing from a macro perspective. The photographs (Fig. 2) showed that the control sample (films untreated with EGDE) underwent considerable dimensional shrinkage, showing varied length and width, after hygrothermal ageing. In contrast, the composite films with different EGDE concentrations exhibited negligible dimensional changes after ageing, indicating that they possessed substantial resistance to hygrothermal ageing.

Fig. 2
figure 2

Change in the length of the EGDE–gelatine composite films before (a–e) and after (a1–e1) hygrothermal ageing: a, a1 control, b, b1 0.5% EGDE, c, c1 1.0% EGDE, d, d1 1.5% EGDE, and e, e1 2.0% EGDE

Full size image

The effect of EGDE on the swelling properties of the gelatine films was also investigated by recording changes in the mass of the films with different EGDE concentrations before and after ageing [28]. The results (Fig. 3) indicated that the swelling ratio of the control sample sharply decreased following hygrothermal ageing. This reduction in weight swelling ratio may be attributed to hygrothermal ageing affecting the distribution of hydrophilic and hydrophobic functional groups on the gelatine film’s surface, resulting in the aggregation of hydrophilic groups and exposure of hydrophobic groups. Figure 3a shows that the weight swelling ratio decreased following EGDE modification, and this decline continued with increasing EGDE concentration, albeit the overall change was minimal. Figure 3b shows that the weight swelling ratio of the control sample reached 672.1% after hygrothermal ageing. With increasing EGDE concentration, the weight swelling ratio gradually decreased to 2% before and after ageing. These results demonstrate that EGDE enhances the hygrothermal stability of the gelatine films.

Fig. 3
figure 3

Weight swelling ratio (a) and its variation (b) for the gelatine films before and after hygrothermal ageing as a function of EGDE concentration in the films

Full size image

Although photographic gelatin is a solid layer, gelatine also presents strong hygroscopicity and swelling, and EGDE and water could formulate an emulsion to be sprayed onto the surface of the gelatine film through the swelling effect into the gelatine layer, then play a role in crosslinking and plasticizing, and ultimately realize the restoration and protection of gelatine-based cultural heritage, the application research results will be embodied in the subsequent publications.

Mesoscopic structure

To further explore the effect of EGDE on the porosity of the gelatine films at a micro–mesoscale level, the control film and composite films with different EGDE concentrations were freeze-dried and SEM analysis was performed to assess changes in pore. The results (Fig. 4a–e) showed considerable porosity of the control film. After treatment with varying concentrations of EGDE, a notable reduction in the pore size was observed and the large pores progressively diminished. Comparison of Fig. 4a and a1 indicates that the pore size of the gelatine films was substantially reduced following hygrothermal ageing. The composite films with different concentrations of EGDE almost retained their surface morphologies and pore structures before and after hygrothermal ageing, corroborating the observed changes in macroscopic sizes and weight swelling ratios as influenced by the EGDE treatment; this result was also consistent with the conclusions derived from Fig. 3.

Fig. 4
figure 4

SEM images of the EGDE–gelatine composite films before (a–e) and after (a1–e1) hygrothermal ageing: a, a1 control, b, b1 0.5% EGDE, c, c1 1.0% EGDE, d, d1 1.5% EGDE, and e, e1 2.0% EGDE

Full size image

Low-field nuclear magnetic resonance (NMR) is a method with unique sensitivity to pore water, as it is based on the magnetization and relaxation behaviour of the spin magnetic moment of hydrogen atoms forming water molecules [38]. As illustrated in Fig. 5, the control film and composite films treated with various EGDE concentrations exhibited three peaks in the T2 inversion spectrum, corresponding to bound water, capillary water and free water within the gelatine films [6, 39], which are arranged according to increasing relaxation times in the T2 spectrum. The signal intensity in the spectrum indicates the water content, with free water predominantly located in the macropores [6]. Figure 5a shows that the highest signal intensity in the T2 spectrum of the control film appears near a relaxation time of 1000 ms, indicating that the control film primarily possessed a macroporous structure, wherein free water was distributed. With increasing EGDE concentration, the relaxation time in the T2 spectrum gradually shifted to 100 ms, indicating the disappearance of the large pore structure associated with free water and its transformation into a smaller pore structure representing capillary water. This relaxation time tended to stabilise with further increase in the EGDE concentration. Figure 5b shows that the relaxation time of the control film after ageing was centred at ~ 100 ms in the T2 spectrum, indicating that hygrothermal ageing altered the pore structure of the control film. However, the pore structure of the composite films treated with varying EGDE concentrations showed minimal changes before and after ageing. Combining these results with the SEM results, it is speculated that EGDE facilitates the transition of the pore structure of the gelatine films from a large to small scale and the EGDE–gelatine composite films exhibit notable stability during hygrothermal ageing.

Fig. 5
figure 5

NMR spectra of the EDGE–gelatine composite films before (a) and after (b) hygrothermal ageing as a function of the EGDE concentration of the films

Full size image

Surface properties

To examine changes in the surface hydrophilicity and hydrophobicity of the EGDE–gelatine composite films before and after hygrothermal ageing, static optical contact angle tests were conducted on the control film and composite films with varying EGDE concentrations before and after hygrothermal ageing [40,41,42]. The results are depicted in Fig. 6. A lower contact angle suggests increased hydrophilicity. Figure 6a reveals that the control film and composite films with different EGDE concentrations initially exhibited hydrophilic properties. As the EGDE concentration increased, the contact angle progressively decreased, enhancing the hydrophilicity of the film surfaces. This enhancement is likely due to the hydrolysis of the epoxy end-groups of EGDE molecules or their ring-opening reactions with the amino groups of gelatine, leading to the formation of abundant hydroxyl groups, thereby considerably increasing the hydrophilicity of the films. Figure 6b shows that the contact angle of the control film after hygrothermal ageing was as high as 118.4°, indicating increased hydrophobicity. However, the contact angles of the composite films after ageing, while being generally higher than those before ageing, ranged between 60.2° and 68.1°, indicating retained hydrophilicity. This implies that EGDE can enhance the hydrophilicity of gelatine films even after hygrothermal ageing, improving their flexibility.

Fig. 6
figure 6

Contact angle test images of the EGDE–gelatine composite films before (a–e) and after (a1–e1) hygrothermal ageing: a, a1 control, b, b1 0.5% EGDE, c, c1 1.0% EGDE, d, d1 1.5% EGDE and e, e1 2.0% EGDE

Full size image

Gelatine films exhibit a typical crystalline structure, with characteristic peaks at 2θ = 7.8° and 22°, representing helical structures in the gelatine molecule [43, 44]. The sharp peak at 2θ = 8° correlates with the diameter and number of gelatine triple helices, while the broad peak at 2θ = 20° pertains to the amorphous region related to the distance between amino acid residues along the helix. Figure 7a illustrates that the EGDE treatment considerably affected the crystallinity of the gelatine films: with increasing EGDE concentration, the peak intensity at 2θ = 7.8° gradually diminished until the peak disappeared and the broad peak at 2θ = 22° weakened until it stabilised. As shown in Fig. 7b, the crystallisation peak of the control sample vanished after hygrothermal ageing and the amorphous peak notably weakened. Conversely, the composite films with varying EGDE concentrations largely retained their pre-ageing structure. This persistence is likely due to EGDE molecules being integrated in the gelatine macromolecular network, obstructing the formation of a gelatine crystalline structure, thereby enhancing the mobility and flexibility of gelatine molecules and effectuating the plasticisation of the gelatine films. In addition, the composite films maintained the pre-ageing amorphous molecular structure after hygrothermal ageing, showing preserved stable configuration.

Fig. 7
figure 7

XRD spectra of the EDGE–gelatine composite films before (a) and after (b) hygrothermal ageing as a function of the EGDE concentration of the films

Full size image

To elucidate the interactions between EGDE and gelatine molecules, the results from FTIR spectroscopic analyses of the control sample and composite films are presented in Fig. 8. The infrared spectra of the control sample [28, 45] features the stretching vibration peak of the carbonyl group in the amide I band at 1650 cm−1, N–H in-plane deformation vibration peak in the amide II band at 1550 cm−1 and C–N stretching vibration peak in the amide III band at 1236 cm−1. Figure 8a shows that for different EGDE concentrations, the composite films preserved the characteristic peak of the gelatine protein amide bond, with a distinct C–O stretching vibration peak emerging at 1084 cm−1. As the EGDE concentration increased, this peak also showed a slightly increased intensity, possibly due to the epoxy end-groups of the EGDE molecules progressively accumulating on the film surfaces. Figure 8b reveals that the typical characteristic peaks of the control sample diminished after hygrothermal ageing, likely due to the aggregation of gelatine proteins, which diminished the intensity of the peaks of side chain groups. The composite films maintained a very typical gelatine characteristic peak, indicating that EGDE molecules could sustain the structural stability of gelatine molecules under hygrothermal ageing. After hygrothermal ageing, there was a decrease in the intensity of the characteristic peak at 1084 cm−1 in the composite films, indicating partial consumption of the C–O bond in the epoxy group at the end of the EGDE molecule. This could be attributed to the migration of small EGDE molecules from the surface to the interior of gelatine under a high-temperature and high-humidity condition, preserving the structural integrity of gelatine molecules.

Fig. 8
figure 8

FTIR spectra of the EDGE–gelatine composite films before (a) and after (b) hygrothermal ageing as a function of the EGDE concentration of the films

Full size image

Mechanical property

The stress–strain curves [46] of the control film and composite films with different EGDE concentrations before and after hygrothermal ageing are presented in Fig. 9. Figure 9a depicts the curve before ageing; the control sample exhibited a maximum strain of 4.2% and stress of 64.2 MPa. As the EGDE concentration increased, the maximum stress and strain of the composite films decreased. At an EGDE concentration of 0.5%, the maximum strain and stress values were 26.0% and 70.2 MPa, respectively. At 1.0% concentration, the maximum stress remained unchanged and strain decreased to 15.1%. Higher EGDE concentrations of 1.5% and 2.0% led to a considerable reduction in the stress and strain values. This indicates that a low EGDE concentration enhances the synergistic effects of its crosslinking and plasticising functions, improving the film’s mechanical properties. However, excessive EGDE may compromise the strength of gelatine films, leading to a considerable reduction in the maximum stress. Figure 9b illustrates the stress–strain curve after ageing. After hygrothermal ageing, the control sample exhibited severe shrinkage and deformation, making it impossible to obtain a stress–strain curve. As the EGDE concentration increased, the maximum stress of the composite films gradually decreased while the strain increased, likely due to EGDE molecules gradually migrating within the gelatine molecular system during ageing, acting as plasticisers. Therefore, the optimal EGDE concentration is recommended to be between 0.5 and 1.0%.

Fig. 9
figure 9

Stress–strain curves of the EDGE–gelatine composite films before (a) and after (b) hygrothermal ageing as a function of the EGDE concentration of the films

Full size image

Conclusion

This study focused on the physical and chemical stabilities of EGDE–gelatine composite films under hygrothermal ageing, which is a critical aspect in the preservation of gelatine-based cultural heritage. The comprehensive evaluation undertaken herein addressed aspects such as macroscopic size, mesoscopic structure, surface properties and mechanical properties. Results indicated that EGDE molecules stabilize the macroscopic sizes, swelling ratios, pore structures and distribution of gelatine films; maintain their hydrophilicity and molecular structures; and improve the stress–strain properties of the films under hygrothermal conditions. The synergistic effects of EGDE’s crosslinking and plasticising functions considerably improve the hygrothermal ageing resistance of the composite films. These results provide theoretical support for using EGDE in the restoration and protection of gelatine-based cultural heritage, with ongoing research focused on practical applications in photo restoration, the findings of which will be detailed in subsequent publications.

Availability of data and materials

All data are available on request. No datasets were generated or analysed during the current study.

Abbreviations

EGDE:

Ethylene glycol diglycidyl ether

RH:

Relative humidity

T:

Temperature

FTIR:

Fourier transform infrared

XRD:

X-ray diffraction

SEM:

Scanning electron microscopy

References

  1. Casoli A. Research on the organic binders in archaeological wall paintings. Appl Sci. 2021;11:9179.

    Article  CAS  Google Scholar 

  2. He X, Li J, Tao L, Zhang B, Fan Z, Su B. Mechanisms of preservation damage: restoration materials affecting salt distribution and soil expansion in wall paintings of Dunhuang. Archaeol Anthrop Sci. 2019;11:5171–9.

    Article  Google Scholar 

  3. Kosel J, Ropret P. Overview of fungal isolates on heritage collections of photographic materials and their biological potency. J Cult Herit. 2021;48:277–91.

    Article  Google Scholar 

  4. Ali MA, Ali MF, Ciliberto E, Greco E, Mello D, Viscuso E. A new method for the preparation of gelatine nanolayer: a possible approach to the in situ consolidation of damaged gelatine photographic emulsions. Appl Phys A. 2016;122:552.

    Article  Google Scholar 

  5. Tomšová K, Ďurovič M. Influence of disinfection methods on the stability of black and white silver gelatine prints. J Cult Herit. 2017;24:78–85.

    Article  Google Scholar 

  6. Liu J, Chen R, Yang J, Li Y, Hu D. Historical photo curling and fracture mainly caused by the surface performance change of gelatine resulting from alternating dry–wet environment. J Cult Herit. 2023;61:57–64.

    Article  Google Scholar 

  7. Liu J, Li Y, Hu D, Chao X, Zhou Y, Wang J. An essential role of gelatine in the formation process of curling in long historical photos. Polymers. 2021;13(22):3894.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  8. Mugnaini G, Gelli R, Mori L, Bonini M. How to cross-link gelatine: the effect of glutaraldehyde and glyceraldehyde on the hydrogel properties. ACS Appl Polym Mater. 2023;5:9192–202.

    Article  CAS  Google Scholar 

  9. Scopel BS, Pretto GL, Corrêa JIP, Baldasso C, Dettmer A, Santana RMC. Starch-leather waste gelatine films cross-linked with glutaraldehyde. J Polym Environ. 2020;28:1974–84.

    Article  CAS  Google Scholar 

  10. Martucci JF, Accareddu AME, Ruseckaite RA. Preparation and characterization of plasticized gelatine films cross-linked with low concentrations of glutaraldehyde. J Mater Sci. 2012;47:3282–92.

    Article  CAS  Google Scholar 

  11. Mohammadzadehmoghadam S, Dong Y. Fabrication and characterization of electrospun silk fibroin/gelatine scaffolds crosslinked with glutaraldehyde vapor. Front Mater. 2019;6:91.

    Article  Google Scholar 

  12. Shrivastava A, Gundiah N. Methylglyoxal crosslinking increases the fracture toughness of gelatine hydrogels. Mech Mater. 2023;176: 104524.

    Article  Google Scholar 

  13. Lin L, Regenstein JM, Lv S, Lu J, Jiang S. An overview of gelatine derived from aquatic animals: properties and modification. Trends Food Sci Technol. 2017;68:102–12.

    Article  CAS  Google Scholar 

  14. Mohtar NF, Perera CO, Hemar Y. Chemical modification of New Zealand hoki (Macruronus novaezelandiae) skin gelatine and its properties. Food Chem. 2014;155:64–73.

    Article  CAS  PubMed  Google Scholar 

  15. Kim D-H, Han J-H, Kwon H-C, Lim S-J, Han S-G, Jung H-S, Lee K-H, Kang J-H, Han S-G. Toxicity assessment of a single dose of poly(ethylene glycol) diglycidyl ether (PEGDE) administered subcutaneously in mice. Toxics. 2021;9(12):354.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  16. Kono H, Nakamura T, Hashimoto H, Shimizu Y. Characterization, molecular dynamics, and encapsulation ability of β-cyclodextrin polymers crosslinked by polyethylene glycol. Carbohydr Polym. 2015;128:11–23.

    Article  CAS  PubMed  Google Scholar 

  17. Tavsanli B, Okay O. Preparation and fracture process of high strength hyaluronic acid hydrogels cross-linked by ethylene glycol diglycidyl ether. React Funct Polym. 2016;109:42–51.

    Article  CAS  Google Scholar 

  18. Chisca S, Falca G, Musteata VE, Boi C, Nunes SP. Crosslinked polytriazole membranes for organophilic filtration. J Membr Sci. 2017;528:264–72.

    Article  CAS  Google Scholar 

  19. Vasylieva N, Barnych B, Meiller A, Maucler C, Pollegioni L, Lin J-S, Barbier D, Marinesco S. Covalent enzyme immobilization by poly(ethylene glycol) diglycidyl ether (PEGDE) for microelectrode biosensor preparation. Biosens Bioelectron. 2011;26:3993–4000.

    Article  CAS  PubMed  Google Scholar 

  20. Li F, Nie M, He X, Fei J, Ding Y, Feng B. Direct electrochemistry and electrocatalysis of hemoglobin on a glassy carbon electrode modified with poly (ethylene glycol diglycidyl ether) and gold nanoparticles on a quaternized cellulose support. A sensor for hydrogen peroxide and nitric oxide. Microchim Acta. 2014;181:1541–9.

    Article  CAS  Google Scholar 

  21. Belfer S, Purinson Y, Fainshtein R, Radchenko Y, Kedem O. Surface modification of commercial composite polyamide reverse osmosis membranes. J Membr Sci. 1998;139:175–81.

    Article  CAS  Google Scholar 

  22. Chisca S, Marchesi T, Falca G, Musteata V-E, Huang T, Abou-Hamad E, Nunes SP. Organic solvent and thermal resistant polytriazole membranes with enhanced mechanical properties cast from solutions in non-toxic solvents. J Membr Sci. 2020;597: 117634.

    Article  CAS  Google Scholar 

  23. Czerner M, Prudente M, Martucci JF, Rueda F, Fasce LA. Mechanical behavior of cold-water fish gelatine gels crosslinked with 1,4-butanediol diglycidyl ether. J Appl Polym Sci. 2020;137:48985.

    Article  CAS  Google Scholar 

  24. Wende FJ, Gohil S, Nord LI, Karlsson A, Kenne AH, Sandström C. Insights on the reactivity of chondroitin and hyaluronan toward 1,4-butanediol diglycidyl ether. Int J Biol Macromol. 2019;131:812–20.

    Article  CAS  PubMed  Google Scholar 

  25. Zhang T, Zhao S, Chen Y, Wang J, Zhang W, Liu J, Kan Y, Li J, Guo X, Li H. In-depth characterization of 1,4-butanediol diglycidyl ether substituted hyaluronic acid hydrogels. Carbohydr Polym. 2023;307: 120611.

    Article  CAS  PubMed  Google Scholar 

  26. Yao X, Liu H, Li C. Development of eco-friendly soy meal adhesives enhanced by ethylene glycol diglycidyl ether. Adv Polym Technol. 2019;2019:8697047.

    Article  Google Scholar 

  27. Silva TL, Silva MGC, Vieira MGA. Palladium adsorption on natural polymeric sericin-alginate particles crosslinked by polyethylene glycol diglycidyl ether. J Environ Chem Eng. 2021;9: 105617.

    Article  Google Scholar 

  28. Liu J, Yang J, Li Y, Hu D, Chen R. Effect of glycerol triglycidyl ether on the dimensional stability and flexibility of photographic gelatine films. Herit Sci. 2023;11:49.

    Article  CAS  Google Scholar 

  29. Vargas G, Acevedo JL, López J, Romero J. Study of cross-linking of gelatine by ethylene glycol diglycidyl ether. Mater Lett. 2008;62:3656–8.

    Article  CAS  Google Scholar 

  30. Al-Hassan AA. Development and characterization of gelatin films derived from camel skin: effects of camel age and plasticizes. J Food Meas Charact. 2022;16:4896–903.

    Article  Google Scholar 

  31. Vo TS, Vo TTBC, Tran TT, Pham ND. Enhancement of water absorption capacity and compressibility of hydrogel sponges prepared from gelatin/chitosan matrix with different polyols. Prog Nat Sci. 2022;32(1):54–62.

    Article  CAS  Google Scholar 

  32. Ma X, Qiao C, Wang X, Yao J, Xu J. Structural characterization and properties of polyols plasticized chitosan films. Int J Biol Macromol. 2019;135:240–5.

    Article  CAS  PubMed  Google Scholar 

  33. van der Sman RGM. Phase separation, antiplasticization and moisture sorption in ternary systems containing polysaccharides and polyols. Food Hydrocolloid. 2019;87:360–70.

    Article  Google Scholar 

  34. Uitto JM, Verbeek CJR, Bengoechea C. Shear and extensional viscosity of thermally aggregated thermoplastic protein. J Appl Polym Sci. 2020;137(45):49393.

    Article  CAS  Google Scholar 

  35. Avallone PR, Romano M, Sarrica A, Delmonte M, Pasquino R, Grizzuti N. Effect of sugars on gelation kinetics of gelatin gels. Fluids. 2022;7:163.

    Article  CAS  Google Scholar 

  36. Yunoki S, Mogi A, Mizuno K, Nagakawa Y, Hiraoka Y. Plasticizer–gelatin mixed solutions as skin protection materials with flexible-film-forming capability. Heliyon. 2024;10(3): e25441.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  37. Kozłowska J, Skopińska-Wiśniewska J, Kaczmarek-Szczepańska B, Grabska-Zielińska S,  Makurat-Kasprolewicz B, Michno A, Ronowska A, Wekwejt M. Gelatin and gelatin/starch-based films modified with sorbitol for wound healing. J Mech Behav Biomed. 2023;148: 106205.

    Article  Google Scholar 

  38. Soto Bravo F, Zhang C. A critical mini-review on the low-field nuclear magnetic resonance investigation of pore coupling effects in near-surface environments. Front Water. 2023;5:1059128.

    Article  Google Scholar 

  39. Zhu Y, Ouyang W, Lu B, Lu S, Feng S, Lu J. Rehydration characteristics of dried icefish (Salangidae) with different drying methods by low-field nuclear magnetic resonance and magnetic resonance imaging. J Food Process Eng. 2024;47(1): e14511.

    Article  CAS  Google Scholar 

  40. Yasuda T, Okuno T, Yasuda H. Contact angle of water on polymer surfaces. Langmuir. 1994;10(7):2435–9.

    Article  CAS  Google Scholar 

  41. Bialopiotrowicz T, Jańczuk B. Surface properties of gelatin films. Langmuir. 2000;18(24):9462–8.

    Article  Google Scholar 

  42. Zhao J, Pan F, Li P, Zhao C, Jiang Z, Zhang P, Cao X. Fabrication of ultrathin membrane via layer-by-layer self-assembly driven by hydrophobic interaction towards high separation performance. ACS Appl Mater Interfaces. 2013;5(24):13275–83.

    Article  CAS  PubMed  Google Scholar 

  43. Pereda M, Ponce AG, Marcovich NE, Ruseckaite RA, Martucci JF. Chitosan-gelatine composites and bi-layer films with potential antimicrobial activity. Food Hydrocolloid. 2011;25(5):1372–81.

    Article  CAS  Google Scholar 

  44. Awasthi SK, Bajpai SK, Utiye AS, Mishra B. Gelatine/poly(aniline) composite films: synthesis and characterization. J Macromol Sci A. 2016;53(5):301–10.

    Article  CAS  Google Scholar 

  45. Manshor NM, Rezali MI, Jai J, Yahya A. Effect of plasticizers on physicochemical and mechanical properties of chitosan-gelatin films. IOP Conf Ser Mater Sci Eng. 2018;358: 012040.

    Article  Google Scholar 

  46. Yang C, Kim Y, Ryu S, Gu GX. Prediction of composite microstructure stress-strain curves using convolutional neural networks. Mater Des. 2020;189: 108509.

    Article  Google Scholar 

Download references

Acknowledgements

The authors would like to thank the conservators in the Second Historical Archives of China for their contributions.

Funding

This research is supported by the National Natural Science Foundation of China (22202129, 62105194), the Key Research and Development Program of Shaanxi Province, China (2024GX-YBXM-559, 2024GX-YBXM-409), 2023 State Administration of Cultural Heritage Science and Technology Research Project (2023ZCK028), and the Fundamental Research Funds for the Central Universities (G2022KY05101).

Author information

Authors and Affiliations

  1. Key Laboratory of Archaeological Exploration and Cultural Heritage Conservation Technology (Ministry of Education), Institute of Culture and Heritage, Northwestern Polytechnical University, Xi’an, 710072, Shaanxi, China

    Jiaojiao Liu, Wenqiang Dong, Junchang Yang & Jing Cao

  2. State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an, 710072, Shaanxi, China

    Zhongwei Chen

  3. School of Materials Science and Engineering, Xi’an University of Science and Technology, Xi’an, 710054, Shaanxi, China

    Ran Chen

Authors
  1. Jiaojiao Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Wenqiang Dong
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Junchang Yang
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Zhongwei Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Jing Cao
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Ran Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

JL and RC conceived the project. JL performed the experiments and wrote the original manuscript. JY, WD, ZC and JC assisted in sample testing and data analysis. RC provided support and guidance for this study, and revised the original manuscript. All authors read and approved the final manuscript.

Corresponding authors

Correspondence to Jiaojiao Liu or Ran Chen.

Ethics declarations

Competing interests

The authors declare no competing interests.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated in a credit line to the data.

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, J., Dong, W., Yang, J. et al. Enhancement of the hygrothermal ageing properties of gelatine films by ethylene glycol diglycidyl ether. Herit Sci 12, 297 (2024). https://doi.org/10.1186/s40494-024-01413-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1186/s40494-024-01413-z

Keywords