Stf16 450

Thermal debinding was done using an ashing furnace (type AAF, Carbolite/Gero, Germany). Sintering was done using a tube furnace (type STF16/450, Carbolite/Gero, Germany) at a temperature of 1300 °C and a pressure of 5 × 10⁻² mbar with a heating rate of 3 K min⁻¹. The parameters for thermal debinding and sintering can be found in Supplementary Table 1.
Fabrication of 3D-printed clamp: The designed clamp for connecting tubing to the glass chip was manufactured using a 3D printer (ProJet MJP 2500/2500 Plus, 3D systems, U.S.) from VisiJet^® M2R-CL resin.

The cluster concentration involved in each experiment corresponds to a theoretical 5 wt % metal loading on the support directly after ligand removal. In a typical experiment, 8.7 mg of cluster 3, for example, was stirred with 95 mg of CNF–PPh₂ or MWNT–PPh₂ in a 1:1 (v/v) mixture of toluene and dichloromethane (total volume of 20 mL) at room temperature for 5 days in the dark. The solid was filtered out, washed with dichloromethane and dried at room temperature under vacuum. The anchoring yield was measured by direct analysis of the metal in the solid samples by ICP-AES. The anchoring yield is defined as the ratio between the amount of metal determined by ICP analysis of the solid and the known amount of metal engaged at the start in solution.
The supported clusters were then submitted to thermal treatment in a tubular oven, STF 16/450 from Carbolite. The samples were placed into porcelain combustion boats and heated under N₂ stream at 300 °C for 1 h for cluster 1 to 4, at 350 °C for 1 h for cluster 5 to 8 and at 400 °C for cluster 9 (heating ramp rate: 100 °C/h).

Thermal debinding of the cured Glassomer green parts was carried out in an ashing furnace (type AAF, Carbolite Gero, Germany) at 600 °C. The brown parts were sintered in a tube furnace (type STF16/450, Carbolite/Gero, Germany) at 1300 °C and a pressure of 5 × 10⁻² mbar. $Y_s=1-{\left(\frac{\Phi }{{\rho }_t/{\rho }_f}\right)}^{\frac{1}{3}}$
The theoretical shrinkage Y_s is calculated by Eq. (1) which depends on the solid loading Φ, the final density ρ_f, and the theoretical density ρ_t of the produced part. The actual shrinkage was determined by measuring the parts in the green state, in sintered state and after metal replication using the digital microscope model VHX 6000 from Keyence (Japan).