ABSTRACT
We synthesized high-heat-resistant adhesives based on metal - organic frameworks owing to their high decomposition temperature and the absence of a glass transition. Heat-resistance tests were performed on adhesive joints consisting of zeolitic imidazolate framework (ZIF)-67-based adhesives and a copper substrate. The as-synthesized ZIF-67-based adhesive exhibited heat resistances at 600 and 700°C in air and nitrogen atmospheres, respectively, comparable to those of conventional high-heat-resistant polymer-based adhesives. The degradation mechanism of the ZIF-67 adhesives was investigated, and their high heat resistance was attributed to the stable existence of the ZIF-67 qtz phase in the adhesive layer at high temperatures without the formation of voids. Thus, adhesives based on ZIF-67 and other metal - organic frameworks can be applied in high-temperature industrial systems.
By focusing on its high thermal stability and absence of glass transition, the ZIF-67 gel was found to have high potential that is comparable to existing heat-resistant adhesives.
ABSTRACT
Metal-organic frameworks (MOFs)/coordination polymers are promising materials for gas separation, fuel storage, catalysis, and biopharmaceuticals. However, most applied research on MOFs is limited to these functional materials thus far. This study focuses on the potential of MOFs as structural adhesives. A sintering technique is applied to a zeolitic imidazolate framework-67 (ZIF-67) gel that enables the joining of Cu substrates, resulting in a shear strength of over 30 MPa, which is comparable to that of conventional structural adhesives. Additionally, systematic experiments are performed to evaluate the effects of temperature and pressure on adhesion, indicating that the removal of excess 2-methylimidazole and the by-product (acetic acid) from the sintered material by vaporization results in a microstructure composed of large spherical ZIF-67 crystals that are densely aggregated, which is essential for achieving a high shear strength.
ABSTRACT
In this study, we investigate the sintering behavior and mechanisms of metal-organic frameworks/coordination polymers (CPs) through physical and microstructural characterization of [Zn(HPO4)(H2PO4)2]·2H2Im (ZPI; a melting CP, Im = imidazole) and ZIF-8 (a non-melting CP). By performing simple compaction and subsequent sintering, a bulk body of CPs was obtained without losing the macroscopic crystallinity. The sintering behavior was found to be dependent on the temperature, heating rate, and physical properties of the CPs and, in particular, their meltability. During sintering, shrinkage occurred in both the CPs, but the observed shrinkage rate of the ZPI was in the 10-20% range, whereas that of the ZIF-8 was less than 1%. Additionally, the sintering mechanisms of the ZPI and ZIF-8 varied between low and high temperatures, and in the case of ZPI, localized melting between the primary particles was the dominant mechanism on the high-temperature side. However, substantial shrinkage did not correspond to an increase in density; on the contrary, a decrease in the apparent density of ZPI was observed as the sintering temperature was increased. The sintering technique is well established and commercially available; thus, the results obtained in this study can be utilized for optimizing the manufacturing conditions of melting CPs.
