A refractory composition for forming a working lining in a metallurgical vessel contains a coarse-grain refractory particle fraction and a fine-grain refractory particle fraction, or at least 0.25% additive calcium oxide, or at least 0.25% titanium dioxide. The coarse-grain refractory particles can include alumina particles, magnesia particles, magnesium aluminate spinel particles, zirconia particles, or doloma particles, or a combination of any of these particles. The fine-grain refractory particles can be comprised of any low-magnesia refractory oxide. The refractory composition can be applied to a metallurgical vessel by spraying, gunning, shotcreting, vibrating, casting, troweling, or positioning preformed refractory shapes, or a combination of any of these techniques. When contacted by molten metal, the molten metal penetrates into the refractory material, wetting the coarse-grain refractory particles, and forming a refractory-metal composite barrier layer that decreases or blocks oxygen transport through the refractory lining.