Multifunctional Polymeric Coatings for Stone Heritage: Hydrophobic–Antimicrobial Mechanisms and Field Performance

Stone heritage deteriorates through physical, chemical, and biological processes driven by water, climate, and microbial colonization. Multifunctional polymeric coatings combining hydrophobic and antimicrobial moieties have emerged as a promising conservation strategy, yet a substantial gap remains between laboratory innovation and real-world performance. This review critically examines advances from 2021 to 2026, covering wetting theory, antimicrobial mechanisms, and material architectures, including molecularly integrated systems, Sol–Gel hybrids, nanocomposites, and layered systems. Long-term studies on the Aurelian Walls in Rome and stone in Reims show that biocidal efficacy typically declines within one to two years despite the chemical persistence of the coatings. In parallel, hydrophobic performance often deteriorates over time due to UV exposure, particulate deposition, and surface chemical changes, leading to increased wettability and reduced protective efficiency. Substrate porosity governs durability and visual compatibility (ΔE* < 5 threshold), while treatments can reshape microbial communities, favoring stress-tolerant meristematic fungi. Regulatory pressure on fluorinated compounds drives the development of more sustainable alternatives. Emerging directions include stimuli-responsive systems, self-healing materials, slippery interfaces, and precision polymer architectures. However, future progress will depend on tailoring formulations to major lithotypes, improving compatibility with porous substrates, and validating performance through standardized accelerated aging and multi-year field trials. Bridging laboratory design with environmental exposure data and conservation practice will be essential for achieving durable and culturally acceptable protection strategies.