K-Means is a clustering algorithm, which is a part of unsupervised machine learning. It is used to create clusters out of lots of unlabeled data points where data holding a similar property or pattern are stored in the same cluster.
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KNN
KNN is a classification algorithm of supervised Learning. It is used to classify a data point to a certain class, based on its property and patterns, for example, if you have two classes, Dog, and Cat and you passed an image of a cat then it will be classified as a cat class.
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