*Review* **Polyaniline/Biopolymer Composite Systems for Humidity Sensor Applications: A Review**

**Yuriy A. Anisimov <sup>1</sup> , Richard W. Evitts <sup>2</sup> , Duncan E. Cree 3,\* and Lee D. Wilson 1,\***


**Abstract:** The development of polyaniline (PANI)/biomaterial composites as humidity sensor materials represents an emerging area of advanced materials with promising applications. The increasing attention to biopolymer materials as desiccants for humidity sensor components can be explained by their sustainability and propensity to absorb water. This review represents a literature survey, covering the last decade, which is focused on the interrelationship between the core properties and moisture responsiveness of multicomponent polymer/biomaterial composites. This contribution provides an overview of humidity-sensing materials and the corresponding sensors that emphasize the resistive (impedance) type of PANI devices. The key physicochemical properties that affect moisture sensitivity include the following: swelling, water vapor adsorption capacity, porosity, electrical conductivity, and enthalpies of adsorption and vaporization. Some key features of humidity-sensing materials involve the response time, recovery time, and hysteresis error. This work presents a discussion on various types of humidity-responsive composite materials that contain PANI and biopolymers, such as cellulose, chitosan and structurally related systems, along with a brief overview of carbonaceous and ceramic materials. The effect of additive components, such as polyvinyl alcohol (PVA), for film fabrication and their adsorption properties are also discussed. The mechanisms of hydration and proton transfer, as well as the relationship with conductivity is discussed. The literature survey on hydration reveals that the textural properties (surface area and pore structure) of a material, along with the hydrophile–lipophile balance (HLB) play a crucial role. The role of HLB is important in PANI/biopolymer materials for understanding hydration phenomena and hydrophobic effects. Fundamental aspects of hydration studies that are relevant to humidity sensor materials are reviewed. The experimental design of humidity sensor materials is described, and their relevant physicochemical characterization methods are covered, along with some perspectives on future directions in research on PANI-based humidity sensors.

**Keywords:** humidity sensor; polyaniline; biopolymer; hydration; adsorption; electrical conductivity; response/recovery time; hysteresis; sensing mechanism; hydrophilicity/hydrophobicity
