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Cooling
Menthol is widely used to create a cooling sensation. Biofreeze cream currently lists menthol 10% as its active ingredient.
Warming
Capsaicin can create a burning or warming sensation and works through a different mechanism. Camphor may be used in counterirritant formulas and can contribute to warming/cooling sensory effects.
Which feels better
Preference is personal. Choose based on the product label, your skin sensitivity, the location of discomfort and any medical considerations.