Multiphase segmentation of pore-scale features and identification of mineralogy from digital images of materials is critical for many applications in the natural resources sector. However, the materials involved (rocks, catalyst pellets, and synthetic alloys) have complex and unpredictable composition. Algorithms that can be extended for multiphase segmentation of images of these materials are relatively few and very human-intensive. Challenges lie in designing algorithms that are context free, can function with less training data, and can handle the unpredictability of material composition. Semisupervised algorithms have shown success in classification in situations characterized by limited training data; they use unlabeled data in addition to labeled data to produce classification. The segmentation obtained can be more accurate than fully supervised learning approaches. This work proposes using a semisupervised clustering algorithm named Continuous Iterative Guided Spectral Class Rejection (CIGSCR) toward multiphase segmentation of digital scans of materials. CIGSCR harnesses spectral cohesion, splitting the intensity histogram of the input image down into clusters. This splitting provides the foundation for classification strategies that can be implemented as postprocessing steps to get the final segmentation. One classification strategy is presented. Micro-computed tomography scans of rocks are used to present the results. It is demonstrated that CIGSCR successfully enables distinguishing features up to the uniqueness of grayscale values, and extracting features present in full image stacks (3D), including features not presented in the training data. Results including instances of success and limitations are presented. Scalability to data sizes $ \mathcal{O}\left({10}^9\right) $ voxels is briefly discussed.