Guoming Liu

Magnetic field-induced martensitic transformation and large magnetoresistance in NiCoMnSb alloys

Magnetic field-induced martensitic transformation was realized in Ni50−xCoxMn39Sb11 alloys. The partial substitution of Co for Ni has turned the antiferromagnetically aligned Mn moments in the starting material Ni50Mn39Sb11 into a ferromagnetic ordering, raising the magnetization at room temperature from 8emu∕g for NiMnSb to ∼110emu∕g for Ni41Co9Mn39Sb11. In the same quaternary sample, a magnetization difference up to 80emu∕g was measured across the martensitic transformation, and the transformation temperature (T0=259K) could be lowered by 35K under a field of 10T. Also a magnetoresistance over 70% was observed through this field-induced transformation.

Realization of magnetic field-induced reversible martensitic transformation in NiCoMnGa alloys

Effect of a magnetic field on martensitic transformation in the NiCoMnGa alloys was investigated. A field-induced reversible martensitic transformation from the martensitic phase of low magnetization to the parent phase of high magnetization has been realized. The substitution of Co for Ni atoms has turned the magnetic ordering of the parent phase from partially antiferromagnetic to ferromagnetic, resulting in a large magnetization change across the transformation, which dramatically enhances the magnetic field driving force. The transformation temperature can be downshifted by magnetic field at a rate up to 14K∕T in Ni37Co13Mn32Ga18. Other mechanism details were also discussed.

Tailoring Crystallization: Towards High-Performance Poly(lactic acid)

Poly(lactic acid) (PLA) is one of the most promising alternatives for petrochemical-based plastics. Crystallization mediation provides the simplest and most practical approach for enhancing the properties of PLA. Here, recent advances in understanding the relationship between crystalline structure and properties of PLA are summarized. Methods for manipulating crystallization towards high-performance PLA materials are introduced.

Crystallization behaviors of n-octadecane in confined space: crossover of rotator phase from transient to metastable induced by surface freezing.

In this paper, the confined crystallization and phase transition behaviors of n-octadecane in microcapsules with a diameter of about 3 microm were studied with the combination of differential scanning calorimetry (DSC), temperature dependent Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD). The main discovery is that the microencapsulated n-octadecane crystallizes into a stable triclinic phase via a mestastable rotator phase (R I), which emerges as a transient state for the bulk n-octadecane and is difficult to be detected by the commonly used characterization methods. As evident from the DSC measurement, a surface freezing monolayer, which is formed at the interface between the microcapsule inner wall and n-octadecane, induces the crossover of the R I from transient to metastable. We argue that the existence of the surface freezing monolayer decreases the nucleating potential barrier of the R I phase, and consequently the lower relative nucleation barrier in the confined geometry turns the transient R I phase into a metastable one.

Crystallization Features of Normal Alkanes in Confined Geometry

How polymers crystallize can greatly affect their thermal and mechanical properties, which influence the practical applications of these materials. Polymeric materials, such as block copolymers, graft polymers, and polymer blends, have complex molecular structures. Due to the multiple hierarchical structures and different size domains in polymer systems, confined hard environments for polymer crystallization exist widely in these materials. The confined geometry is closely related to both the phase metastability and lifetime of polymer. This affects the phase miscibility, microphase separation, and crystallization behaviors and determines both the performance of polymer materials and how easily these materials can be processed. Furthermore, the size effect of metastable states needs to be clarified in polymers. However, scientists find it difficult to propose a quantitative formula to describe the transition dynamics of metastable states in these complex systems. Normal alkanes [CnH2n+2, n-alkanes], especially linear saturated hydrocarbons, can provide a well-defined model system for studying the complex crystallization behaviors of polymer materials, surfactants, and lipids. Therefore, a deeper investigation of normal alkane phase behavior in confinement will help scientists to understand the crystalline phase transition and ultimate properties of many polymeric materials, especially polyolefins. In this Account, we provide an in-depth look at the research concerning the confined crystallization behavior of n-alkanes and binary mixtures in microcapsules by our laboratory and others. Since 2006, our group has developed a technique for synthesizing nearly monodispersed n-alkane containing microcapsules with controllable size and surface porous morphology. We applied an in situ polymerization method, using melamine-formaldehyde resin as shell material and nonionic surfactants as emulsifiers. The solid shell of microcapsules can provide a stable three-dimensional (3-D) confining environment. We have studied multiple parameters of these microencapsulated n-alkanes, including surface freezing, metastability of the rotator phase, and the phase separation behaviors of n-alkane mixtures using differential scanning calorimetry (DSC), temperature-dependent X-ray diffraction (XRD), and variable-temperature solid-state nuclear magnetic resonance (NMR). Our investigations revealed new direct evidence for the existence of surface freezing in microencapsulated n-alkanes. By examining the differences among chain packing and nucleation kinetics between bulk alkane solid solutions and their microencapsulated counterparts, we also discovered a mechanism responsible for the formation of a new metastable bulk phase. In addition, we found that confinement suppresses lamellar ordering and longitudinal diffusion, which play an important role in stabilizing the binary n-alkane solid solution in microcapsules. Our work also provided new insights into the phase separation of other mixed system, such as waxes, lipids, and polymer blends in confined geometry. These works provide a profound understanding of the relationship between molecular structure and material properties in the context of crystallization and therefore advance our ability to improve applications incorporating polymeric and molecular materials.

Crystallization Behavior of Binary Even-Even n-Alkane Mixtures in Microcapsules: Effect of Composition and Confined Geometry on Solid-Solid phase Separation

The crystallization behaviors of binary even-even normal alkane (n-alkane) mixtures (n-C(18)H(38)/n-C(20)H(42), abbreviated as C(18)/C(20)) with different compositions, both in the bulk state and in nearly monodisperse microcapsules, have been investigated by the combination of differential scanning calorimetry and temperature-dependent X-ray diffraction. The solid-solid phase separation, usually observed during the cooling process of bulk samples, is greatly suppressed and even eliminated after being microencapsulated, with the orthorhombic-ordered phase dominating in the low-temperature crystal. Such a crystallization transition is attributed to the special interaction between the two even n-alkanes and the confined environment in microcapsules. The triclinic ordered phase, solely formed by the single even n-alkanes (C(18) or C(20)), becomes less stable due to the weakening of the layered structure and the suppression of the terminal methyl-methyl interactions in the confined geometry, which favors the miscibility of the two components. Furthermore, besides the chain-length difference and the composition, the confined environment is proved to be another important factor to exert strong positive influence on suppressing the solid-solid phase separation of C(18)/C(20) binary system.

Effective activation of halloysite nanotubes by piranha solution for amine modification via silane coupling chemistry

The present work reports a novel modification methodology for halloysite nanotubes (HNTs) that includes two successive steps, i.e., activation by piranha solution and silanization reaction. A commercial silane coupling agent, 3-aminopropyltriethoxysilane (APS), was selected to modify the surface of HNTs. The presence of APS moieties on the HNT surface was characterized by the combination of Fourier transform infrared (FTIR) spectroscopy, thermogravimetry (TGA), X-ray diffraction (XRD), transmission electron microscopy (TEM) and nitrogen sorption. For the coupling reaction, the effect of reaction time, temperature, rehydration and APS concentration on the course of silanization degree was carefully investigated. The mechanism and the grafted product structure of the reaction between activated HNTs and APS were revealed through 29Si solid-state NMR spectroscopy and XPS analysis. The result shows that piranha solution is an effective activation agent for silanization of HNTs. A higher reaction temperature (120 °C) contributed to a higher grafted amount compared with a lower temperature (70 °C). Moisture led to a higher degree of silanization. The grafted amount increased with APS concentration and leveled off at about 1%. Further increase in the APS concentration only led to a drastic decrease in grafting yield. The grafting reaction was confirmed by the presence of tridentate (T3) and bidentate (T2) bonded Si in 29Si NMR. Free terminal amino groups and protonated amine groups were identified in modified HNTs by XPS.

Phase change materials of n-alkane-containing microcapsules: observation of coexistence of ordered and rotator phases

In the present investigation, the crystallization and phase transition behaviours of normal alkane (n-docosane) in microcapsules with a mean diameter of 3.6 μm were studied by the combination of differential scanning calorimetry (DSC), temperature-dependent X-ray diffraction (XRD) and variable-temperature solid-state nuclear magnetic resonance (VT solid-state (13)C NMR). The DSC and VT solid-state (13)C NMR results reveal that a surface freezing monolayer is formed prior to the bulk crystallization of the microencapsulated n-docosane. More interestingly, it is confirmed that after the bulk crystallization, the ordered triclinic phase coexists with the rotator phase I (RI) for the microencapsulated n-docosane. We argue that the reduction of the free energy difference between the two phases, resulting from the microencapsulation process, leads to the coexistence of the ordered triclinic and rotator phases of the normal alkanes.

Two-way shape memory property and its structural origin of cross-linked poly(ε-caprolactone)

In this work, two-way shape memory (TWSM) properties and the corresponding structural origin of cross-linked poly(e-caprolactone) (cPCL) with different gel contents obtained by adopting different weight percentages of benzoyl peroxide (BPO) were investigated. The effects of gel contents on melting temperatures, crystallization temperatures and crystallinity of the cPCL materials were studied with differential scanning calorimetry. The TWSM properties of the samples were determined by dynamic mechanical analysis. It was found that gel content was the key factor determining the TWSM behavior, and higher gel content would result in the so-called robust TWSM effect for cPCL samples (cPCLx, x denoting the weight percentage of BPO). Compared with cPCL10, cPCL5 had larger elongation and lower recovery capabilities due to its lower gel content. However, the sample with much lower gel content (cPCL3) displayed almost no TWSM behavior, implying that an appropriate gel content was responsible for the TWSM characteristic. The crystalline structure of cPCLx subsequently changed when subjected to external stress. As the samples were cooled down under constant stress, higher stress would lead to a more oriented crystalline structure. Furthermore, concurrent wide-angle and small-angle X-ray scattering investigations revealed the structural evolution occurring during the TWSM process, indicating that the crystal orientation along the stretching direction took place simultaneously with the elongation during the cooling process.

A coupling of martensitic and metamagnetic transitions with collective magneto-volume and table-like magnetocaloric effects

A coupling of the first-order paramagnetic-to-induced-ferromagnetic martensitic and the second-order antiferromagnetic-to-ferromagnetic metamagnetic transitions was found in MnNi0.8Fe0.2Ge alloy. Based on the coupling, a magneto-volume effect driven by the martensitic transition and a table-like magnetocaloric effect generated by the successive magnetic phase transitions arise collectively. By using the magneto-volume effect, the internal stress in the volume-expansion martensitic transition was determined at 350 MPa. The magnetocaloric effect, with a wide working temperature range of 26 K around room temperature, shows a small hysteresis loss (5 J kg−1) and a large net refrigerant capacity (157 J kg−1).