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A low temperature plasma nitriding process has become one of the most promising methods to make solid-solution hardening by the nitrogen super-saturation, being free from toxicity and energy consumption. High-density radio-frequency and direct current (RF/DC) plasma nitriding process was applied to synthesize the nitrided AISI304 microstructure and to describe the essential mechanism of inner nitriding in this low temperature nitriding (LTN) process. In case of the nitrided AISI304 at 673 K for 14.4 ks, the nitrided layer thickness became 66.5 μm with the surface hardness of 1550 HV and the surface nitrogen content of 9 mass%. This inner nitriding process was governed by the synergetic interrelation among the nitrogen super-saturation, the lattice expansion, the phase transformation, the plastic straining, the microstructure refinement, and the acceleration of nitrogen diffusion. When this interrelation is sustained during the nitriding process, the original austenitic microstructure is homogeneously nitrided to have fine-grained microstructure with the average size of 0.1 μm. Once this interrelation does not work anymore, the homogeneous microstructure changed itself to the heterogeneous one. The plastic straining took place in the selected coarse grains so that the parts of them were only refined. This plastic localization accompanied with the localized phase transformation.