Umeå universitets logga

The transition behavior and thermal properties of nylon-6 at elevated pressure, p, have been established by in-situ thermal conductivity, κ, and heat capacity measurements. The glass transition temperature, T_g, of virgin nylon-6 is described well by the empirical equation T_g(p) = 319.60(1 + 1.90 p)^0.24 (p in GPa and T_g in K). Moreover, isobaric heating in the 1−1.2 GPa range causes a cold-crystallization transition near 500 K. As a result, κ increased 15% whereas the heat capacity per unit volume decreased 7% slowly with time during 4 h annealing at 530 K. The transformation is associated with a significantly increased crystallinity, from 35% to 55−60%, and a pressure-induced preferred orientation and increased size for the lamellae of monoclinic α crystalline structure. This state has 8−10 K higher melting temperature and better formic acid resistance than that of virgin nylon-6. However, the results show no indication of cross-linking, as reported for similarly treated nylon-1010 and nylon-11, but instead chain scissoring.

Transition behavior and thermal properties of a multi-wall carbon nanotube (MWCNT)/nylon-6 composite (P-composite) made by in situ polymerization and subsequently structurally modified by high-pressure–high-temperature treatment have been established. The thermal conductivity (κ) of nylon-6 improved 27% by the addition of 2.1 wt.% MWCNT filler simultaneously as the heat capacity per unit volume decreased 22% compared with that of nylon-6 at 1 atm and 298 K. Moreover, the MWCNT filler raises the glass transition temperature (T_g) of nylon-6, but the pressure dependence of T_g remains unchanged. A model for κ indicates that the interfacial thermal resistance between the MWCNT filler and the nylon-6 matrix decreases 20% up to 1 GPa and most significantly above 0.8 GPa. P-composite was structurally modified by a sluggish cold-crystallization transition at 1.0 GPa, 530 K, which further increased κ by as much as 37% as the crystallinity of nylon-6 improved from 31% to 58% with a preferred crystal orientation and increased crystal size.

Multi-wall carbon nanotube (MWCNT)/nylon-6 composites made by in-situ polymerization and subsequently modified by treatment at 1.0 GPa (or 1.7 GPa) and 530 K have been studied by WAXD, DSC and NMR. The pressure treatment gives an amorphous to crystalline transformation where the crystallinity increases from ∼31% to as much as ∼58% concurrently as the nylon-6 crystals increase in size and attain a preferred orientation relative to the applied pressure. A composite of 2.1 wt% purified MWCNT in nylon-6 shows significantly higher melting temperature than neat nylon-6 after identical pressure treatments. The improved thermal stability of the composite is attributed to crystal growth in the presence of reinforcing MWCNTs. The NMR spectrum of a pressure treated composite is similar to that of nylon-6 single crystals, which suggests a reduction of crystal boundaries after treatment, but there is no indication of covalent bonds between the nylon-6 chains and the MWCNTs.

Polyisoprene (PI)/single-wall carbon nanotube (SWCNT) composites and pure PI have been cross-linked by high-pressure treatment to yield densified elastomeric states. Simultaneously, the SWCNT and cross-linked-induced changes of the thermal conductivity, heat capacity per unit volume, and glass transition were investigated by in situ measurements. The thermal conductivity of both the elastomeric and liquid PI improves ≈120% by the addition of 5 wt % SWCNT filler. The SWCNT filler (5 wt %) increases the glass-transition temperature of liquid PI by ≈7 K and that of the elastomeric state by as much as 12 K, which is due to a filler-induced increase in the cross-link density. Moreover, the 5 wt% filler yields a heat capacity decrease by ≈30% in both the glassy and liquid/elastomeric states, which indicates that SWCNTs cause a remarkably large reduction of both the vibrational and configurational heat capacity of PI. Finally, the consequences of high-pressure densification and the possibilities this provides to help elucidating the nature of the heat conduction in polymer/carbon nanotube composites are discussed.

High-viscosity liquid cis-1,4 polyisoprene (PI), with up to 20 wt % single-wall carbon nanotubes (SWCNTs), has been cross-linked by high pressure and high temperature (HP&HT) treatment at 513 K and pressures in the range 0.5 to 1.5 GPa to yield densified network polymer composites. A composite with 5 wt % SWCNTs showed 2.2 times higher tensile strength σ_UTS (σ_UTS = 17 MPa), 2.3 times higher Young’s modulus E (E = 220 MPa) and longer extension at break than pure PI. The improvement is attributed to SWCNT reinforcement and improved SWCNT−PI interfacial contact as a result of the HP&HT cross-linking process, and reduced brittleness despite a higher measured cross-link density than that of pure PI. The latter may originate from an effect similar to crazing, i.e., bridging of microcracks by polymer fibrils. We surmise that the higher cross-link densities of the composites are due mainly to physical cross-links/constraints caused by the SWCNT−PI interaction, which also reflects the improved interfacial contact, and that the CNTs promote material flow by disrupting an otherwise chemically cross-linked network. We also deduce that the PI density increase at HP&HT cross-linking is augmented by the presence of CNTs.

The thermal conductivity κ, heat capacity per unit volume ρc_p and glass transition behaviour under pressure have been established for medium and high vinyl content polybutadiene PB with molecular weights 2600 and 100 000 and their highly cross-linked (ebonite) states obtained purely by high-pressure high-temperature treatments. Cross-linking eliminates the glass transitions and increases κ by as much as 50% at 295 K and 1 atm, and decreases ρc_p to a limiting level close to that of the glassy state of PB, which is reached before the ultimate cross-link density is achieved. The pressure and temperature behaviours of κ are strongly changed by cross-links, which increases the effect of temperature but decreases the effect of pressure. We attribute these changes to a cross-linked induced permanent densification and consequential increase of phonon velocity simultaneously as conduction along polymer chains is disrupted. The glass transition temperatures for a time scale of 1 s are described to within 0.5 K by: T_g(p) = 202.5 (1 + 2.94 p)^0.286 and T_g(p) = 272.3 (1 + 2.57 p)^0.233 (p in GPa and T in K) up to 1 GPa, for PB2600 and PB100000, respectively, and can be estimated for medium and high vinyl content PBs with molecular weights in between by a constant, pressure independent, shift in temperature.

In a comprehensive investigation of carbon nanotube (CNT) filled liquid and solid polybutadienes of molecular weights 2600 and 100000, respectively, we report results of thermal conductivity (κ), glass transition temperature (T_g), interfacial interaction and microstructure before and after simultaneous high-pressure and high-temperature (HP&HT) treatment. The HP&HT treatment changed polybutadiene from a liquid or solid to a highly cross-linked, ebonite-like, state. Concurrently, the microstructure changed from randomly dispersed CNTs to a web-like structure of coated and/or wrapped CNTs, with a permanent shift in their D*-band by as much as 16 cm⁻¹. Moreover, κ of the recovered state of a 2.9 wt% –COOH functionalized multi-wall carbon nanotube (MWCNT) composite increased by 34% predominantly due to an irreversible densification and a consequentially increased phonon velocity. Results prior to treatment show that single-wall carbon nanotube (SWCNT) fillers promote κ better (17%/wt%) than –SH functionalized MWCNT fillers (8%/wt%), which is accounted for by their higher aspect ratio, whereas their about twice as high κ appears to be unimportant. The SWCNTs also raise T_g slightly more than MWCNTs and, in particular, under the most densified conditions and for the high molecular weight polybutadiene, which may be due to more favorable conditions for coating/wrapping.