Explosive spalling of ultra-high performance concrete (UHPC) at elevated temperatures is one of the main problems limiting its application. While the intrinsic mechanism governing the spalling is determined by the UHPC matrix. Therefore, in this paper, multi-technique characterization approaches, i.e., acoustic signal characteristics, fractal characteristics of spalling fragments, and thermal cracks are employed to quantitatively characterize the spalling of the UHPC matrix. The effects of moisture content, heating rate, geometric characteristics of specimens, mineral admixtures, crumb rubber content, and fibers on concrete spalling are investigated to reveal the explosive spalling mechanism, reduce the risk of explosive spalling, and develop a spalling-resistant material. The waveform, cumulative energy, and spectrum of the spalling acoustic signal are used to assess the intensity of concrete spalling. The results show that the UHPC matrix with high moisture content, high heating rate, and large specimen size undergoes violent spalling events characterized by larger amplitude and smaller frequencies of acoustic signals. Incorporating crumb rubber increases the spalling events in the frequency range of 8000–10000 Hz, which plays a positive role in alleviating spalling. Meanwhile, the fractal characteristics of spalling fragments and thermal cracks can also quantitatively reflect the intensity of concrete spalling (i.e., the larger the fractal dimension, the more severe spalling). By minimizing the moisture content and heating rate, as well as increasing rubber content, the spalling fragments can be larger and the fractal dimension can be reduced. It is also found that saturated specimens spall with significant cumulative energy. While the specimens with a large size and low moisture content spall with lower cumulative energy and an increase in the proportion of spalling fragments in the small particle size range. A higher heating rate and larger specimens can induce a higher thermal stress, which can be more likely to spall explosively. While a lower moisture content can result in explosive spalling at a higher heating rate. Hence, it is believed that thermal stress can be the dominant factor affecting explosive spalling and the moisture content can be an accelerator. The addition of multi-scale fibers completely prevents explosive spalling by releasing vapor pressure from the channels created by fiber melting and improving the tensile strength of concrete, which also effectively restricts the thermal cracking of UHPC due to their hybrid bridging effects.
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