Volume fraction of fibre and matrix is nothing but the cross sectional areal fractions. Assume your composite specimen has a cross section of 20mm width and 10mm thickness. Cross sectional area is 200mm2. If the fibre occupies 120mm2 and the matrix 80mm2, then the fibre areal/volume fraction is 120/200=0.6 or 60%. Balance matrix/polymer is 40%.
Thermal Conductivity of Composite = VF of Fibre x Thermal Conductivity of Fibre + VF of Matrix x Thermal Conductivity of Matrix.
TC of Composite = 0.6 x TC of Fibre + 0.4 x TC of Matrix.