Synchrotron Radiation Wide-angle X-ray Research Articles

The Role of Lanthanum Stearate on Strain-Induced Crystallization and the Mechanical Properties of Whole Field Latex Rubber.

Natural rubber (NR) is extensively utilized in numerous industries, such as aerospace, military, and transportation, because of its exceptional elasticity and all-around mechanical qualities. However, commercial NR made using various techniques typically has distinct mechanical characteristics. For instance, whole field latex rubber (SCR-WF) cured with accelerator 2-Mercaptobenzothiazole exhibits poor mechanical properties. This work attempts to enhance the mechanical property of SCR-WF via the addition of lanthanum stearate (LaSt). The influence of LaSt on strain-induced crystallization (SIC) and the mechanical properties of SCR-WF were investigated. The results of crosslinking density measured by the equilibrium swelling method demonstrate that the presence of LaSt significantly increases the crosslinking density of SCR-WF with lower loading of LaSt. The results of the mechanical properties show that the introduction of LaSt can enhance the tensile strength and fracture toughness of SCR-WF. To reveal the mechanism of LaSt improving the mechanical properties of SCR-WF, synchrotron radiation wide-angle X-ray diffraction (WAXD) experiments were used to investigate the SIC behaviors of SCR-WF. We found that the LaSt leads to higher crystallinity of SIC for the strain higher than 3.5. The tube model indicates the contribution of LaSt in both crosslinking and topological constraints. This work may provide an instruction for developing SCR-WF with superior mechanical properties.

Temperature-Dependent Polymorphism and Phase Transformation of Friction Transferred PLLA Thin Films.

Poly(L-lactic acid) (PLLA) thin films with a highly oriented structure, successfully prepared by a fast friction transfer technique, were investigated mainly on the basis of synchrotron radiation wide-angle X-ray diffraction (WAXD) and Fourier transform infrared spectroscopy (FTIR). The crystalline structure of the highly oriented PLLA film was remarkably affected by friction transfer temperatures, which exhibited various crystal forms in different friction temperature regions. Interestingly, metastable β-form was generated at all friction transfer temperatures (70-140 °C) between Tg and Tm, indicating that fast friction transfer rate was propitious to the formation of β-form. Furthermore, the relative content among β-, α'-, and α-forms at different friction temperatures was estimated by WAXD as well as FTIR spectroscopy. In situ temperature-dependent WAXD was applied to reveal the complicated phase transition behavior of PLLA at a friction transfer temperature of 100 °C. The results illustrated that the contents of β- and α'-forms decreased in turn, whereas the α-form increased in content due to partially melt-recrystallization or crystal perfection. Moreover, by immersing into a solvent of acetone, β-, α'-form were transformed into stable α-crystalline form directly as a consequence. The highly oriented structure was maintained with the chain perfectly parallel to friction transfer direction after acetone treatment, evidenced by polarized FTIR and polarized optical microscopy (POM) measurements.

In situ wide-angle X-ray scattering study on the change of microcrystalline structure in Jincheng anthracite during high-temperature carbonization

Carbonization is an effective way to achieve the comprehensive utilization of coal. However, the in situ variation of graphite-like microcrystals, the basic structure of coal macromolecules, with heating and cooling during carbonization has not been fully characterized so far. Anthracite is a type of humic coal with the highest degree of coalification, and its structure change can be monitored well by X-ray scattering or diffraction techniques. In this contribution, an in situ synchrotron radiation wide-angle X-ray scattering (WAXS) study on high-temperature (1200°C) carbonization of a high-quality anthracite mined in Jincheng, China, is presented. The results show that, during the continuous process of heating and cooling, the size and height of the aromatic lamellae first decrease and then increase with minima at 900 and 1000°C, respectively, while the interlayer spacing first increases and then decreases with a maximum at 1000°C. The roadmap of graphite-like microcrystalline structure change during the whole continuous process of heating and cooling is revealed and described.

In Situ SAXS and WAXD Investigations of Polyamide 66/Reduced Graphene Oxide Nanocomposites During Uniaxial Deformation.

Epitaxial crystallization between Polyamide 66 (PA66) and reduced graphene oxide (RGO) can enhance the interfacial interaction and the mechanical properties of PA66/RGO nanocomposites. In situ two-dimensional synchrotron radiation wide angle X-ray diffraction and small angle X-ray scattering were used to track the structural evolution of the PA66/RGO nanocomposites with an epitaxial crystal during uniaxial deformation. In the PA66/RGO nanocomposites, the structural evolution of non-epitaxial and epitaxial crystals could be clearly analyzed. The non-epitaxial crystal, whose crystal plane can slip, shows the rearrangement and the Brill transition during uniaxial deformation. While the PA66 chains of an epitaxial crystal are held by RGO, the crystal plane could therefore not slip. The epitaxial crystal also constrains the deformation of the amorphous phase and the crystal form transition of non-epitaxial crystals around them. With the content increase of epitaxial crystals, the constraint effect becomes more obvious. Therefore, the rigid epitaxial crystals in the PA66/RGO nanocomposites promote mechanical properties. The present findings can deepen the understanding of structural evolution during the tensile deformation of PA66/RGO nanocomposites and the influence of the epitaxial crystals on the mechanical property in semicrystalline polymers with a H-bond.

Effect of flame retardant on the microfine structures and creep behavior of polyester industrial yarns

The respective underlying mechanisms of the creep behavior and microstructure evolution in the creep process of an ordinary high-tenacity (HT) poly(ethylene terephthalate) (PET) industrial yarn and a flame retardant high-tenacity (FRHT) polyester industrial yarn are identified in this article. Synchrotron radiation wide-angle X-ray scattering (WAXS) and small-angle X-ray scattering (SAXS), birefringence test, FTIR were employed to investigate and compare the supramolecular, micro–nano and conformation structures of the two yarns after creep. The results showed that, under the same creep condition, the creep deformation of FRHT was larger and the creep recovery was lower than those of HT. The creep deformation of the two yarns mainly took place in amorphous region with different mechanisms, and their changes in the crystal region in terms of crystal orientation and crystallinity were slightly. HT yarns had high crystallinity and amorphous orientation, and the creep was mainly reversible elastic creep with a high-elastic recovery rate. By contrast, there was more irreversible plastic creep for FRHT yarns due to the lower initial crystallinity and amorphous orientation, which play a key role in the creep deformation.

Stretch-Induced Reverse Brill Transition in Polyamide 46

Structural transitions of polyamide 46 (PA46) films during the tensile stretch at temperatures from 37 to 249 °C were studied using in situ synchrotron radiation wide-angle X-ray diffraction (SR-WAXD) and Fourier transform infrared (FTIR) techniques. The structural evolution during the stretch at different temperatures can be roughly divided into three regions. In region I (37 ≤ T < 180 °C), stretch enlarges the d-spacing gap between the (100) and (010/110) planes of α phase (triclinic), which is opposite to that during heating. In region II (180 ≤ T < 230 °C), stretch induces a reverse Brill transition, which is characterized by the single diffraction of γ phase (pseudohexagonal) splitting into two diffractions of α phase, while further increasing the strain drives the two split diffractions to transform to a single broad diffraction. As in situ FTIR measurements reveal the continuously increasing content of trans conformation, we speculate that stretch may induce a new form, which is an intermediate structure close to both α and γ phases (named α′ phase) at large strain. In region III (230 ≤ T ≤ 249 °C), the γ phase may skip the α phase and directly transform into the α′ phase. The nonequilibrium crystal phase diagrams of PA46 were constructed in the strain–temperature space and true stress–temperature space. Current results demonstrate that stretch plays a countereffect of heating on the Brill transition of PA46.

Frustrating Strain-Induced Crystallization of Natural Rubber with Biaxial Stretch.

The supreme mechanical performance of natural rubber (NR) is commonly attributed to strain-induced crystallization (SIC). The SIC of NR during uniaxial stretch has been extensively investigated, whereas that under multiaxial deformation has been rarely reported, which is close to real service conditions (i.e., tire). In this work, the crystallization behavior of NR under biaxial stretch was studied with in situ synchrotron radiation wide-angle X-ray diffraction in combination with a custom-built biaxial stretch machine. It is observed that biaxial stretch frustrates the SIC of NR: within λx/λy < 1.6, where λx and λy are stretch ratios of two mutually perpendicular axes, no crystallization emerges even under large drawing ratio until sample fracture at ambient temperature. This finding challenges the common wisdom of the self-reinforcement mechanism of SIC in NR under multiaxial deformation in real service conditions. A theoretical SIC model is proposed, which can decouple the contributions of conformational entropy reduction ΔSf and amorphous chain orientation f to final Gibbs free energy change (ΔG) during multiaxial deformation. This model quantitatively renders a reproduction of the crystallinity during the biaxial stretch, which is well consistent with experimental results and can be further generalized for flow-induced crystallization of semicrystalline polymers.

The Effect of Epoxidation on Strain-Induced Crystallization of Epoxidized Natural Rubber.

The effect of epoxidation on strain-induced crystallization (SIC) of epoxidized natural rubber (ENR) and mechanism are studied with synchrotron radiation wide-angle X-ray diffraction (SR-WAXD) and polarized infrared spectroscopy (P-IR). WAXD results reveal that appropriate epoxidation, for example, ENR-25 epoxidized with ≈25% isoprene units, can unexpectedly enhance the SIC of natural rubber (NR), resulting in the improvement of tear resistance. On the other hand, exorbitant epoxidation, for example, ENR-40 epoxidized with ≈40% isoprene units, depresses the SIC and weakens the mechanical properties of NR remarkably. P-IR studies reveal that epoxidation can promote the orientation of chain segments along the stretching direction, which plays a determining role on SIC of NR. Accordingly, hierarchical multiscale schematic models are proposed. This insight into epoxidation on SIC of ENR strongly suggests that ENR with appropriate epoxidation degree is a promising candidate material for the fabrication of high-performance engineering rubber products.

In situ characterization of strain-induced crystallization of natural rubber by synchrotron radiation wide-angle X-ray diffraction: construction of a crystal network at low temperatures.

Strain-induced crystallization (SIC) of natural rubber (NR) at descending temperatures as low as -60 °C is systematically investigated by in situ synchrotron radiation wide-angle X-ray diffraction (SR-WAXD) measurement. The detailed structural evolution of NR during SIC is studied in the strain-temperature space, where up to four regions are defined depending on the SR-WAXD results. In region I, the molecular chains begin to be oriented under tensile loading. The onset of crystallization happens in the very beginning of region II, and the NR crystal acts as a new physical cross-linking point to form a crystal network, namely the series model. The further increment of crystallinity (> ca. 8%) leads to the transition of the crystal network from the series model to the parallel model in region III. The crystal network is finally accomplished in region IV, where the crystallinity remains almost constant. Interestingly, regions III and IV exist only in the intermediate-temperature zone II (-40 °C to -10 °C), which are missing in zones I (-10 °C to 25 °C) and III (-60 °C to -40 °C). This suggests that sufficient crystallinity (χII-III > ca. 8%) is required to form the parallel model. The new crystal network provides a deep understanding of SIC of NR considering the microscopic features, i.e. oriented amorphous component, the onset of crystallization and crystallinity evolution and its correlation with the macroscopic stress-strain curve.

Understanding structure-mechanics relationship of high density polyethylene based on stress induced lattice distortion

The relationship between the macroscopic non-linear mechanics and the microscopic crystal structural evolution of pre-oriented high-density polyethylene (HDPE) is investigated by in situ synchrotron radiation wide-angle X-ray diffraction (WAXD) measurement over a wide temperature range from −10 to 130 °C. With the concept of stress-induced disordering of crystal, the ratio (φa/b) of lattice parameters a to b is defined as a new structural variable, which can reflect the lattice distortion and then the microscopic stress state of orthorhombic crystal (O-crystal). According to the temperature-dependent non-linear variation of φa/b with strain, the contributions of O-crystal and monoclinic crystal (M-crystal) to the macroscopic mechanics including linear elasticity, yielding, stress softening and strain hardening are clarified. It is found that M-crystal bears the main extensional stress once formed, although it survives within a limited strain window relying on temperature. By further combining the extensional phase diagram constructed in strain-temperature space, the HDPE deformation is recognized to undergo successively one-dimensional (1D) chain segments rotation of crystal, two-dimensional (2D) crystal plan shearing or slipping and three-dimensional (3D) recrystallization along with increasing strain or stress, demonstrating a multiscale structural transition and energy dissipation mechanism.

Stretch-Induced Crystallization and Phase Transitions of Poly(dimethylsiloxane) at Low Temperatures: An in Situ Synchrotron Radiation Wide-Angle X-ray Scattering Study

Stretch-induced crystallization (SIC) and phase transitions of poly(dimethylsiloxane) (PDMS) have been studied with the in situ synchrotron radiation wide-angle X-ray scattering technique (WAXS) du...

Effects of graphene oxide on the strain-induced crystallization and mechanical properties of natural rubber crosslinked by different vulcanization systems

To reveal the influence of graphene oxide (GO) on the mechanical properties of natural rubber (NR) crosslinked by different vulcanization systems, synchrotron radiation wide angle X-ray diffraction (WAXD) experiments were conducted to investigate the strain-induced crystallization (SIC) behaviors of the NR/GO nanocomposites. We found that the sulfur/accelerator (S/A) ratio in the vulcanization recipes is a critical factor which determines the SIC behaviors of the NR/GO nanocomposites: lower S/A ratio leads to higher crystallization rate of SIC. The tube model has been used to analyze the network structure of the NR/GO nanocomposites. The results demonstrate that the presence of GO more significantly increases the crosslinking density of the nanocomposites with lower S/A ratio. A possible mechanism has been proposed to interpret this phenomenon: during the curing process, the hydroxyl and carboxyl groups on the surface of GO could react with the vulcanization accelerator first and eventually form additional crosslinks in the vicinity of the GO sheets. This work may provide an instruction for developing GO filled rubber materials with superior mechanical properties.

Protective action of trehalose and glucose on protein hydration shell clarified by using X-ray and neutron scattering

Sugars are well known to retain protein structures and to protect denaturation. Protective actions of sugars on protein structures have been discussed under issues of preferential hydration and/or interaction between sugar and protein. By using synchrotron radiation wide-angle X-ray scattering (SR-WAXS) and small-angle neutron scattering (SANS) methods, we have succeeded to obtain a direct evidence of the effect of trehalose and glucose on a protein structure and hydration. Myoglobin from horse-skeletal muscles was used as one of typical globular proteins. The sugars used were trehalose and glucose whose concentrations were varied from 0% w/w to 35% w/w. The experimental SR-WAXS and SANS data combined with theoretical scattering function simulation and fitting clearly show that both sugars are preferentially excluded from the hydration-shell region of the protein to preserve hydration-shell density. up to the sugar concentration of ∼25% w/w. Compared with that of glucose (monosaccharide), the preservation action of the protein hydration-shell is much evidently seen for the case of trehalose (disaccharide), which might relate to a role of the preferential production of trehalose by organisms against extreme environmental stress.

In situ synchrotron radiation X-ray diffraction studies on molecular aggregation structure of nylon 12 films during bulge testing.

It is desirable to establish a method for evaluating mechanical properties, such as modulus and strength, of micrometer and sub-micrometer thick polymer films. Bulge tests, where bulge deformation is imposed on films by the pressure of an inert gas, are suitable for satisfying this demand. However, very few studies on polymer films exist in the literature. In this study, bulge testing equipment for in situ synchrotron radiation wide-angle X-ray diffraction (WAXD) measurements is designed and used to study the relationship between the molecular aggregation structure and the mechanical properties of a crystalline nylon 12 (Ny12) film during bulge testing. Isothermally crystallized and quenched Ny12 films exhibited stress-strain curves similar to those obtained by conventional uniaxial elongation. In situ WAXD measurements during bulge testing revealed that the lattice extension of the crystallites is clearly dependent on crystallinity. Concretely, crystallites in the isothermally crystallized film show higher elastic properties than those in the quenched one. The results of the molecular aggregation structure, including the crystal structure and the amorphous chain surrounding the crystallites, of the films during bulge deformation firstly obtained in this study must be useful for designing toughened polymer films.

Effects of bamboo cellulose nanowhisker content on the morphology, crystallization, mechanical, and thermal properties of PLA matrix biocomposites

Abstract To improve the mechanical and thermal properties of poly (lactic acid) (PLA) composites, bamboo cellulose nanowhiskers (BCNW) were extracted and introduced into PLA composites as fillers. PLA/BCNW biofilms were fabricated by solution casting with different BCNW contents (0, 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, and 4.0 wt%). The characteristics of the biofilms were investigated by scanning electron microscopy (SEM), mechanical measurements, synchrotron radiation wide-angle X-ray scattering (WAXS) and differential scanning calorimetry (DSC). The results showed that the maximum tensile modulus and elongation at break of 427.72 ± 19.32 MPa and 22.27 ± 3.50% were reached at 2.5 wt% and 1.0 wt% loadings, respectively. Both homogeneity and stereocomplexed crystallites were observed, and heterogeneous nucleation effect was confirmed. With the addition of BCNW, the crystallite size of PLA/BCNW composites increased remarkably, and the largest crystallinity was 30.7 ± 0.9% with 2.5 wt% BCNW. These results provided data support for enlarging the application of PLA.

Microfluidic Dry-spinning and Characterization of Regenerated Silk Fibroin Fibers.

The protocol demonstrates a method for mimicking the spinning process of silkworm. In the native spinning process, the contracting spinning duct enables the silk proteins to be compact and ordered by shearing and elongation forces. Here, a biomimetic microfluidic channel was designed to mimic the specific geometry of the spinning duct of the silkworm. Regenerated silk fibroin (RSF) spinning doped with high concentration, was extruded through the microchannel to dry-spin fibers at ambient temperature and pressure. In the post-treated process, the as-spun fibers were drawn and stored in ethanol aqueous solution. Synchrotron radiation wide-angle X-ray diffraction (SR-WAXD) technology was used to investigate the microstructure of single RSF fibers, which were fixed to a sample holder with the RSF fiber axis normal to the microbeam of the X-ray. The crystallinity, crystallite size, and crystalline orientation of the fiber were calculated from the WAXD data. The diffraction arcs near the equator of the two-dimensional WAXD pattern indicate that the post-treated RSF fiber has a high orientation degree.

Deformation of Ultrahigh Molecular Weight Polyethylene Precursor Fiber: Crystal Slip with or without Melting

Temperature effects on deformation behaviors of extracted ultrahigh molecular weight polyethylene (UHMWPE) precursor fibers are studied with the in situ synchrotron radiation wide-angle X-ray scattering technique (WAXS) during tensile deformation at temperatures from 25 to 130 °C. The structural and mechanical evolution behaviors during tensile deformation can be divided into four temperature regions with boundaries located at temperatures of αI and αII relaxations and the onset of melting, respectively, which reveal that the deformation behaviors of polymer crystals are determined by the interplay between intrinsic structural dynamic or chains mobility and external stress field. Irrespective of temperature, yield and strain-softening proceed via partial melting while crystal slip via cutting crystal planes occurs in the strain-hardening zone. Finally we construct morphological diagrams containing crystallinity, crystal size, and orientation in temperature–strain space, which may serve as a roadmap for UH...

Effect of Draw Ratio on the Microstructure of Silk Fibroin/Graphene Oxide Hybrid Fibers

In order to fabricate high performance artificial silk, hybrid fibers were dry spun from regenerated silk fibroin (RSF) aqueous solution mixed with graphene oxide (GO) nanosheets. The influence of draw ratio on the microstructure and mechanical properties of RSF/GO hybrid fibers was studied through Fourier transform infrared spectroscopy (FT-IR), synchrotron radiation wide-angle X-ray diffraction, Raman spectroscopy and mechanical testing. The results showed that with increasing draw ratio, both amorphous phase and mesophase of the dry-spun artificial fiber gradually converted to crystals. The orientation of crystals and mesophase changed slightly at low draw ratio, but increased significantly at draw ratios of 3 and 4X. The β-sheet content of silk fibroin and the disorder degree of GO sheets in the fibers also increased with the increase of draw ratio. The initial modulus, breaking strength and breaking energy of the hybrid fibers achieved great improvement at a draw ratio of 4X. The structure evolution of the RSF/GO hybrid fibers may benefit the understanding of the structure-property relationship of other composite fibers.

Observations of Enamel Microstructure in Incipient Lesions Remineralized by NaF Dentifrices

Synchrotron Radiation (SR) Wide-angle X-ray Diffraction (WAXD) and Small-angle X-ray Scattering (SAXS) techniques were used to assess microstructure of bovine enamel white-spot lesions (WSL) evaluated in a 10-day pH cycling model comprising three different dentifrice groups: (A) 0.21% NaF plus TCP (Clinpro Tooth Crème), (B) 1.1% NaF plus TCP (Clinpro 5000), or (C) 0% NaF (Tom’s of Maine) dentifrice. Each day consisted of four 2-minute treatments, one 4-hour acid challenge (pH=5.0), and immersion in artificial saliva (pH=7.0) between these events. These specimens were also examined with cross-sectional microhardness, digital light microscopy and FE-SEM (field emission scanning electron microscope), and demonstrated the remineralization model effected changes in subsurface microstructure. X-ray diffraction data from WAXD and SAXS were collected on enamel slab cross-sections extending from 0 μm to 150 μm, in 6 μm microbeam increments. A primary outcome of this observational study was that simultaneous WAXD and SAXS measurements were able to resolve significant differences (ANOVA, Student’s t-test, p&lt;0.05) between the effects of the two fluoridecontaining dentifrices on subsurface lesion microstructure. In particular, enamel lesions treated with 1.1% NaF dentifrice group manifested an abundance of nanometer-sized crystallites, while treatment with the 0.21% NaF dentifrice produced larger apatite-like crystals. While the presence of fluoride in both cases promoted regularity in crystal size and orientation, this was not observed for lesions treated without fluoride. Altogether, our observations demonstrate the pathological processes for remineralization are markedly influenced by the presence and concentration of fluoride, the microstructural characteristics of which can be distinguished using the simultaneous WAXD and SAXS technique.

Cellulose Nanowhiskers from Moso Bamboo Residues: Extraction and Characterization

To take full advantage of moso bamboo processing waste, bamboo cellulose nanowhiskers were isolated from bamboo residues using sulfuric acid hydrolysis. Changes in bamboo cellulose at different stages of processing, as well as the roles of acid concentrations (55 wt% and 65 wt%) and hydrolysis times (1 h to 5 h) on the characteristics of nanowhiskers were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetry-Fourier transform infrared spectroscopy analysis (TGA-FTIR), synchrotron radiation wide angle X-ray scattering (WAXS), composition analysis, and Brunauer-Emmett Teller (BET) analysis. Both rod-like and network-like nanowhiskers were observed. Alkaline pretreatment removed impurities and part of the hemicellulose. Cellulose content increased to nearly 85%, and specific surface area improved as well after bleaching. Nanowhiskers had an average length of 455 nm, diameter of 12 nm, and an aspect ratio of about 37. Cellulose I was the dominant composition in bamboo cellulose; the transformation of cellulose Iα to cellulose Iβ was observed. Nanowhiskers presented greater crystallinity and crystallite size than those of cellulose without hydrolysis, but lower thermal stability. These bionanowhiskers might be used as reinforcements in nanocomposites.