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Chinese, Indians, Mongols and Persians, as early as the 13th century. All rockets used some form of solid or powdered propellant up until the 20th century, when liquid-propellant rockets offered more efficient and controllable alternatives. Solid rockets are still used today in model rockets and on larger applications for their simplicity and reliability.
Since solid-fuel rockets can remain in storage for long periods, and then reliably launch on short notice, they have been frequently used in military applications such as missiles. Solids are, however, frequently used as strap-on boosters to increase payload capacity or as spin-stabilized add-on upper stages when higher-than-normal velocities are required. The medieval Song dynasty Chinese invented the solid-propellant rocket at a time when bows, arrows, and catapult-based projectile launchers were state of the art military technology in medieval Europe.