Thixotropic studies of lead-based solder, lead-free solder and conductive adhesive pastes

The stencil printing process is an important process in the assembly of Surface Mount Technology (SMT)devices. There is a wide agreement in the industry that the paste printing process accounts for the majority of assembly defects. Experience with this process has shown that typically over 60% of all soldering defects are due to problems associated with the flow properties of solder pastes. Therefore, the rheological measurements can be used as a tool to study the deformation or flow experienced by the pastes during the stencil printing process. This paper presents results on the thixotropic behaviour of three pastes; lead-based solder paste, lead-free solder paste and isotropic conductive adhesive (ICA). These materials are widely used as interconnect medium in the electronics industry. Solder paste are metal alloys suspended in a flux medium while the ICAs consist of silver flakes dispersed in an epoxy resin. The thixotropy behaviour was investigated through two rheological test; (i) hysteresis loop test and (ii) steady shear rate test. In the hysteresis loop test, the shear rate were increased from 0.001 to 100s-1 and then decreased from 100 to 0.001s-1. Meanwhile, in the steady shear rate test, the materials were subjected to a constant shear rate of 0.100, 100 and 0.001s-1 for a period of 240 seconds. All the pastes showed a high degree of shear thinning behaviour with time. This might be due to the agglomeration of particles in the flux or epoxy resin that prohibits pastes flow under low shear rate. The action of high shear rate would break the agglomerates into smaller pieces which facilitates the flow of pastes, thus viscosity is reduced at high shear rate. The solder pastes exhibited a higher degree of structural breakdown compared to the ICAs. The area between the up curve and down curve in the hysteresis curve is an indication of the thixotropic behavior of the pastes. Among the three pastes, lead-free solder paste showed the largest area between the down curve and up curve, which indicating a larger structural breakdown in the pastes, followed by lead-based solder paste and ICA. In a steady shear rate test, viscosity of ICA showed the best recovery with the steeper curve to its original viscosity after the removal of shear, which indicating that the dispersion quality in ICA is good because the high shear has little effect on the microstructure of ICA. In contrast, lead-based paste showed the poorest recovery which means this paste undergo larger structural breakdown and dispersion quality in this paste is poor because the microstructure of the paste is easily disrupted by high shear. The structural breakdown during the application of shear and the recovery after removal of shear is an important characteristic in the paste printing process. If the paste’s viscosity can drop low enough, it may contribute to the aperture filling and quick recovery may prevent slumping.

IR/Raman spectroscopy and DFT calculations of cyclic di-amino acid peptides. Part III: comparison of solid state and solution structures of cyclo(L-Ser-L-Ser)

B3-LYP/cc-pVDZ calculations of the gas-phase structure and vibrational spectra of the isolated molecule cyclo(L-Ser-L-Ser), a cyclic di-amino acid peptide (CDAP), were carried out by assuming C-2 symmetry. It is predicted that the minimum-energy structure is a boat conformation for the diketopiperazine (DKP) ring with both L-Beryl side chains being folded slightly above the ring. An additional structure of higher energy (15.16 kJ mol(-1)) has been calculated for a DKP ring with a planar geometry, although in this case two fundamental vibrations have been calculated with imaginary wavenumbers. The reported X-ray crystallographic structure of cyclo(L-Ser-L-Ser), shows that the DKP ring displays a near-planar conformation, with both the two L-Beryl side chains being folded above the ring. It is hypothesized that the crystal packing forces constrain the DKP ring in a planar conformation and it is probable that the lower energy boat conformation may prevail in the aqueous environment. Raman scattering and Fourier-transform infrared (FT-IR) spectra of solid state and aqueous solution samples of cyclo(L-Ser-L-Ser) are reported and discussed. Vibrational band assignments have been made on the basis of comparisons with the calculated vibrational spectra and band wavenumber shifts upon deuteration of labile protons. The experimental Raman and IR results for solid-state samples show characteristic amide I vibrations which are split (Raman:1661 and 1687 cm(-1), IR:1666 and 1680 cm(-1)), possibly due to interactions between molecules in a crystallographic unit cell. The cis amide I band is differentiated by its deuterium shift of ~ 30 cm(-1), which is larger than that previously reported for trans amide I deuterium shifts. A cis amide II mode has been assigned to a Raman band located at 1520 cm(-1). The occurrence of this cis amide II mode at a wavenumber above 1500 cm(-1) concurs with results of previously examined CDAP molecules with low molecular weight substituents on the C-alpha atoms, and is also indicative of a relatively unstrained DKP ring.