Tube/Pipe (TP) 304 stainless steel has been widely used in industry, but a change in its microstructures may endanger its service safety, and it is essential to evaluate its microstructural evolution. In this work, a pulse-echo nonlinear method is proposed to characterize the microstructural evolution of the TP304 stainless steel. The detailed pulse-echo nonlinear experimental process is presented, and it is shown that the absolute nonlinear parameter can be determined when the effect of attenuation is taken into account. The microstructural evolution of TP304 stainless steel is artificially controlled by annealing treatments before it is evaluated by using nonlinear ultrasonic method and metallographic method. The results show that the grain sizes increase as the annealing time increases, which leads to the performance degradation of the TP304 steel and an increase in the nonlinear parameters, with the reason discussed considering the variation in the microstructure. The present pulse-echo nonlinear method is easier to conduct than the traditional transmission-through method and the absolute nonlinear parameter can be determined for quantitative characterization. The variation in determined nonlinear parameters provides a reference to evaluate the microstructural evolution of TP304 stainless steel.Materials 2020, 13, 1395 2 of 11 dislocations, precipitates, and fatigue microcracks [6]. Therefore, nonlinear acoustic testing can be used to characterize the degradation of the microstructural properties of TP 304 stainless steel components.When a monochromic ultrasonic wave is transmitted in a material, the waveform is distorted by the nonlinear elastic property of the material and harmonic waves are generated [7]. The nonlinear ultrasonic method often measures these harmonic waves to obtain the relative or absolute nonlinear parameter to evaluate the microstructural evolution of materials. The typical method uses longitudinal waves and is usually conducted in through-transmission mode, which requires access to both sides; however, this technique may be restrictive in a field measurement scenario where, for example, access is only possible to the outer surface of a pipeline [8]. The pulse-echo method, which enables single-side access to the test component using a nonlinear longitudinal wave, provides a useful tool for practical applications of nonlinear ultrasonic measurement.Determining the absolute nonlinear parameter is important in order to quantitatively evaluate the microstructural evolution of materials [9]. Measuring nonlinear parameters for fluids using the pulse-echo method with a rigid boundary has been reported [10]. For solid materials or structures, the stress-free boundary will destructively alter the nonlinear wave generation process. Some researchers have shown that the 'residual' nonlinear wave reflected from stress-free boundaries can still be measured [8,11]. However, there are some difficulties in determining the absolute nonlinear parameters of TP 304 stainless steel using the pulse-echo method...