Gelatine adhesives, also known as animal glues, are collagen-based water-soluble biopolymers derived from vertebrate connective tissues. One of the various fields in which gelatine adhesives are widely used is the conservation of cultural heritage such as decorated furniture and panel paintings. It is observed that, with time, the failure in these objects often occurs along the adhesive bondlines. Given the moisture and temperature sensitivity of these adhesives, obtaining knowledge of their long-term behaviour, when exposed to climate variations, is pivotal. Here, the influence of hygrothermal ageing (exposure to a combination of elevated temperature and relative humidity (RH) cycling) on the microstructure and macroscopic properties of four different types of gelatine adhesives is investigated. These adhesives were selected from different animal origins namely bovine, rabbit, and fish with different Bloom strengths. It was observed that ageing cycles interfere with the most critical structural feature of protein chains namely triple helices. A clear decay in triple helix content at the micro-scale, determined by Differential Scanning Calorimetry (DSC) and X-Ray Diffraction (XRD) techniques, was observed which had implications on the macroscopic properties of these adhesives such as reduction of strain to failure and toughness (strain energy density to failure). The rate of decay in properties was revealed to be the highest in the adhesives with the lowest triple helix content. This study provides a scientific view of microstructure-property relationships in gelatinous adhesives as a function of environmental ageing, and stipulates the underlying mechanism of the degradation of mechanical properties as the loss of structural triple helices, regardless of the animal origin.@en

Gelatine adhesives aka ‘animal glues’ are water-soluble biopolymers used in historic objects such as wooden cabinets and panel paintings since ancient times. This paper investigates the correlations between microstructural features, namely triple helices, and macroscopic properties of four different types of gelatine adhesives, prevalently used in conservation practices, irrespective of the animal origin. These adhesives include bovine bone, bovine skin, rabbit skin, and fish glues. Thin adhesive films were produced via solution casting methods in controlled climate conditions and their thermal and mechanical properties, and moisture sensitivity were investigated. XRD as a non-destructive characterisation method demonstrated good agreement with DSC in the quantification of gelatine adhesive (animal glue) triple helix content irrespective of the animal origin. Linear correlations between triple helices and gel (Bloom) strength and tensile strain energy to failure (toughness) were found for all adhesive types. Dynamic vapour sorption experiments demonstrated that lower triple helix content is correlated with higher moisture sensitivity of the adhesives. Moreover, the effect of environmental RH on the thermal behaviour of adhesives was investigated by DSC. The results demonstrated that the increase in environmental RH causes a reduction in the adhesives' glass transition and denaturation temperatures whilst triple helix content did not alter. Bovine bone glue with the lowest triple helix content showed the least toughness and highest moisture sensitivity, whilst fish glue with the highest triple helix content was identified as the most flexible glue.

@en

Collagen-based bioadhesives, also known as animal glues, are derived from animal parts (e.g. skin, bone, and cartilage). They have been widely used in the production of decorative wood working, paintings, bookbinding, and other historical objects for centuries as well as for their restoration and preservation [1]. Collagen, in which the term (kólla) is derived from the Greek word for glue, is a fibrous structural protein with a hierarchical microstructure at different length scales. Collagen is water insoluble and can be turned into water-soluble gelatine through the denaturation process. Upon denaturation, the triple helix structure in collagen unwinds and turns into random coils giving gelatinous animal glue. Gelatinous animal glue can be dissolved in water and during gelling and subsequent drying, the random protein coils undergo partial renaturation back into triple helices. These triple helices in the adhesive act as physical cross-links leading to a continuous three-dimensional network structure [2]. These microstructural features affect the physical and mechanical performance of the glue at micro and macro scales. In this study four different adhesives from different animal species both mammalian and fish are investigated. These adhesives are bovine bone, bovine skin, rabbit skin, and fish. For this study, thin films of these adhesives were manufactured using the solution casting method. Physical and mechanical behaviour of the adhesives were characterized using Differential Scanning Calorimetry (DSC), X-ray diffraction (XRD), Bloom strength evaluation, and uniaxial tensile tests. @en