Synchrotron Wide-angle X-ray Diffraction Research Articles

Effect of Sample Geometry on Graphitization of Polyacrylonitrile.

In this study, it is analyzed how sample geometry (spheres, nanofibers, or films) influences the graphitization behavior of polyacrylonitrile (PAN) molecules. The chemical bonding and changes in the composition of these three geometries are studied at the oxidation, carbonization, and graphitization stages via scanning electron microscopy (SEM), in situ thermogravimetric-infrared (TGA-IR) analysis, elemental analysis, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The influence of molecular alignment on the graphitization of the three sample geometries is investigated using synchrotron wide-angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). The effects of molecular alignment at different draw rates during spinning are explored in detail.

Investigation of the Microstructure of PAN Precursor Fibers Obtained at Various Processing Stages

The production of high-performance carbon fibers relies heavily on the structural transformations of polyacrylonitrile (PAN) fiber during processing. In this article differential scanning calorimetry (DSC), synchrotron small-angle X-ray scattering (SAXS), and synchrotron wide-angle X-ray diffraction (WAXD) were used to study the changes of the thermal properties, voids and crystal structure of the PAN precursor fibers on industrial lines during the continuous processing stages, i.e., after the treatment in the coagulation bath, after stretching in boiling water and after stretching in high-temperature steam. The findings of this study suggest that after boiling water stretching the molecular chain motion of the PAN precursor fiber weaken, resulting in the expansion of the voids. After high-temperature steam stretching the voids became elliptical and oriented in the stretching direction. Although the boiling water stretching process partially damaged the (100) crystal planes of the PAN precursor fibers, it does not hinder their overall crystalline structure. The high stretching ratio primarily affected the orientation of the molecular chains. This orientation, even in the context of partial crystal plane disruption, further promoted the crystallization of the (100) crystal planes in the fibers. These experiments explored the correlation between the processing technology and fiber structure transformation of PAN-based carbon fibers, resulting in producing a guide for the preparation of high-performance carbon fibers with fewer defects.

Direct determination of the π-helix structure and helix transition behavior of poly(β-phenethyl l-aspartate) via synchrotron X-ray diffraction.

The helix-sense inversions of poly(β-phenethyl l-aspartate) (2P) and diblock copolymers (2P-3P), with 2P and poly(β-phenylpropyl l-aspartate) (3P) blocks, were studied in their solid states using synchrotron wide-angle X-ray diffraction and small-angle X-ray scattering. The characteristic parameters of the π-helix structure of 2P were directly determined in situ after the helix transition at a high temperature. In the 2P-3P block copolymers, the main chains of the 3P blocks initially convert from right- to left-handed α-helices, and then the 2P blocks convert irreversibly from right-handed α-helices to left-handed π-helices. The chemical structures of the side chains of poly(l-aspartic acid ester)s significantly affect their helix transition behaviors.

Drug-Loaded Nanocarriers Composed of Cholesteryl Oleate Crystal Cores and Multiple-Nanosheet Shells of γ-Cyclodextrin Inclusion Complex Crystals.

In this study, we prepared drug-loaded nanocarriers made of cholesteryl oleate (ChO) and γ-cyclodextrin (γ-CD). A nanosuspension (nanosuspension-I, NS-I) containing nanoparticles with a mean size of approximately 170 nm was obtained through the solvent-diffusion method using ethanol. A second nanosuspension (nanosuspension-II, NS-II), which was prepared by freeze-drying and redispersion of NS-I, exhibited an increased particle size of approximately 210 nm. Cryogenic transmission electron microscopy (cryo-TEM) and atomic force microscopy (AFM) force-distance curves indicated that the nanoparticles in NS-I were oblong and soft. However, those in NS-II were angular and stiff, and, interestingly, multiple nanosheets covered the solid-liquid interface. Synchrotron wide-angle X-ray diffraction (WAXD) analysis of NS-II indicated that the nanoparticles in it had a core-shell structure, where the ChO crystal in the inner core was covered by multiple nanosheets of ChO/γ-CD inclusion complex crystals. The X-ray peak analysis suggested that the γ-CD columns of the nanosheets were vertically stacked onto the ChO crystal interface. It was found that the nanosheets on the nanoparticle interface were formed during the freezing process. A model drug carbamazepine (CBZ) was loaded into the ChO/γ-CD nanoparticles by pre-dissolving CBZ in ethanol during the solvent-diffusion process. Cryo-TEM, 1H NMR, ζ-potentials, and synchrotron WAXD indicated that CBZ was unexpectedly loaded into the shell as a CBZ/γ-CD inclusion complex crystalline nanosheet. The specific nanosheet structure, where ChO and CBZ coexisted in the same crystal of γ-CD, could achieve CBZ loading in the nanoparticles. ChO/γ-CD nanoparticles with the unique core-shell structure are expected to perform as practical carriers for drug delivery.

Electric-Field-Induced Phase Transition and Crystal Structural Change of the Oriented Poly(vinylidene Fluoride) β Form as Clarified by the In Situ Synchrotron Wide-Angle X-ray Diffraction Measurement

Electric-Field-Induced Phase Transition and Crystal Structural Change of the Oriented Poly(vinylidene Fluoride) β Form as Clarified by the <i>In Situ</i> Synchrotron Wide-Angle X-ray Diffraction Measurement

A study on texture stability and the biaxial creep behavior of as-hydrided CWSR Zircaloy-4 cladding at the effective stresses from 55 MPa to 65 MPa and temperatures from 300 °C to 400 °C

The creep rupture of high burnup used nuclear fuel (> 45 GWD/MTU) cladding is regarded as one of the failure mechanisms during long-term dry storage. A high amount of zirconium hydride in the cladding matrix would degrade the mechanical properties of the cladding especially leading to delayed hydride cracking. To better understand the influence of zirconium hydride on the biaxial thermal creep performance and the crystalline texture stability of Zircaloy-4 cladding, the pressurized tube technique is applied to test the durability of the as-hydrided material. Tests were performed on as-received Zircaloy-4 tubular specimens as well as-hydrided ones with targeted 300 wt parts per million (wppm) or 750 wppm hydrogen. The biaxial creep experiments were conducted at temperatures from 300 °C to 400 °C and at equivalent stresses at mid-wall from 55 MPa to 65 MPa. The hydridation process prior to creep tests induces the formation of FCC δ-hydride platelets along the circumferential direction of the tube. This alignment and phase structure of hydride show no significant change after biaxial creep tests. The creep strain-rate negatively depends on the hydrogen content. The synchrotron wide-angle X-ray diffraction (WAXD) technique and electron backscatter diffraction (EBSD) analysis were applied for the study of the crystallographic orientation relationship. zirconium-to-hydride grain orientation follows Shoji–Nishiyama crystallographic relationship. This relationship is stable before and after creep deformation. These results of creep performance and texture stability of Zircaloy-4 claddings can help support the design basis of interim and long-term dry storage facilities.

Laser sintering of PA12 particles studied by in-situ optical, thermal and X-ray characterization

The microstructure of products manufactured by selective laser sintering (SLS) is known to be highly dependent on various process and material parameters. The latter thus also affect the final part properties. While most work has focused on ex-situ characterization of the printed parts, little is known about the time-dependent microstructure development during sintering. In this work, we present direct observations of the microstructural evolution during laser sintering of polyamide 12 (PA12) particle doublets by in-situ synchrotron wide angle X-ray diffraction (WAXD), using our in-house developed laser sintering setup. Simultaneously, the neck growth between the particles and the temperature are captured via optical and infrared microscopy. We show that isothermal crystallization experiments under quiescent conditions are not sufficient to describe crystallization in a non-isothermal process like SLS. The enhanced crystallization kinetics in small particles suggests that both temperature and flow play a role. This finding was corroborated by the critical Weissenberg numbers estimated from rheological reptation and Rouse time scales. Furthermore, a microstructure survey has been carried out by microtoming thin slices of the sintered doublets. Both optical and atomic force microscopy reveal significant differences in the crystalline structure of the laser-affected zone as compared to the un-sintered region.

Chemoenzymatic Polymerization of l-Serine Ethyl Ester in Aqueous Media without Side-Group Protection.

Poly(l-serine) (polySer) has tremendous potential as a polypeptide-based functional material due to the utility of the hydroxyl group on its side chain; however, tedious protection/deprotection of the hydroxyl groups is required for its synthesis. In this study, polySer was synthesized by the chemoenzymatic polymerization (CEP) of l-serine ethyl ester (Ser-OEt) or l-serine methyl ester (Ser-OMe) using papain as a catalyst in an aqueous medium. The CEP of Ser-OEt proceeded at basic pH ranging from 7.5 to 9.5 and resulted in the maximum precipitate yield of polySer at an optimized pH of 8.5. A series of peaks detected by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry revealed that the formed precipitate consisted of polySer with a degree of polymerization ranging from 5 to 22. Moreover, infrared spectroscopy, circular dichroism spectroscopy, and synchrotron wide-angle X-ray diffraction measurements indicated that the obtained polySer formed a β-sheet/strand structure. This is the first time the synthesis of polySer was realized by CEP in aqueous solution without protecting the hydroxyl group of the Ser monomer.

New insight into naturally occurring network and entanglements induced strain behavior of vulcanized natural rubber

Vulcanized natural rubber (NR) with different naturally occurring network and entanglements were prepared by film formation and mechanical mixing methods, and the influences of naturally occurring network and entanglements on stress-strain relation and stain-induced crystallization (SIC) was analyzed by tensile testing machine and in-situ synchrotron wide-angle X-ray diffraction. It was found that there were three types of networks in vulcanized NR, i.e. sulfur crosslinked network, naturally occurring network and entanglements. While mechanical mixing samples had more naturally occurring network leading to higher effective crosslink densities, film forming samples had higher degree of entanglements that facilitate to generate strain-induced crystallization (SIC) and enhance the crystallinity. Entanglements could move quickly and act as pivotal points to align rubber chains, and demonstrate more improvement in mechanical properties. Compared to mechanical mixing samples, tensile strength and elongation at break of film forming samples maximum increased by 55.5% and 20.7%, respectively. This work unveiled the important role of entanglements existed in NR gum, which may give advice on how to protect entanglements in NR gum, thus fabricating high performance vulcanized NR.

Synergistic Effect of Pressurization Rate and β-Form Nucleating Agent on the Multi-Phase Crystallization of iPP.

Using a homemade pressure device, we explored the synergistic effect of pressurization rate and β-form nucleating agent (β-NA) on the crystallization of an isotactic polypropylene (iPP) melt. The obtained samples were characterized by combining small angle X-ray scattering and synchrotron wide angle X-ray diffraction. It was found that the synergistic application of pressurization and β-NA enables the preparation of a unique multi-phase crystallization of iPP, including β-, γ- and/or mesomorphic phases. Pressurization rate plays a crucial role on the formation of different crystal phases. As the pressurization rate increases in a narrow range between 0.6–1.9 MPa/s, a significant competitive formation between β- and γ-iPP was detected, and their relative crystallinity are likely to be determined by the growth of the crystal. When the pressurization rate increases further, both β- and γ-iPP contents gradually decrease, and the mesophase begins to emerge once it exceeds 15.0 MPa/s, then mesomorphic, β- and γ- iPP coexist with each other. Moreover, with different β-NA contents, the best pressurization rate for β-iPP growth is the same as 1.9 MPa/s, while more β-NA just promotes the content of β-iPP under the rates lower than 1.9 MPa/s. In addition to inducing the formation of β-iPP, it shows that β-NA can also significantly promote the formation of γ-iPP in a wide pressurization rate range between 3.8 to 75 MPa/s. These results were elucidated by combining classical nucleation theory and the growth theory of different crystalline phases, and a theoretical model of the pressurization-induced crystallization is established, providing insight into understanding the multi-phase structure development of iPP.

Reversible mesophase in stress-annealed poly(3-hydroxybutyrate) fibers: A synchrotron x-ray and polarized ATR-FTIR study

Structural changes in poly(3-hydroxybutyrate) (P3HB) monofilaments (diameter ~90 μm), induced by annealing under tensile stress (1 h with 1.6–40 MPa loading at 80–130 °C) have been investigated with synchrotron wide-angle x-ray diffraction (WAXD) and polarized attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy. Melt-spun P3HB fibers consist of an amorphous phase, a crystalline α-phase and a mesophase. Specific IR bands in s-polarized (electric field vector along the fiber axis) spectra have been identified to arise from the mesophase. For fibers annealed at low stress (1.6 MPa), the mesophase content practically disappears but can be recovered with tensile drawing. In-situ WAXD and polarized ATR-FTIR studies, performed during cyclic tensile loading/unloading, have revealed that the mesophase formation/dissolution is highly reversible in fibers annealed at low stress. This reversibility behavior, and the lack of off-axis reflections in WAXD patterns, support the theory that the mesophase is made of conformationally disordered and stretched chains, which are mainly located in-between α-crystals.

Direct determination of helix structures involved in the screw-sense reversal of poly(β-phenylpropyl l-aspartate) by synchrotron X-ray diffraction.

The helix-sense reversal of poly(β-phenylpropyl l-aspartate) (3PLA) in the solid state was studied by synchrotron wide-angle X-ray diffraction and small-angle X-ray scattering. The direct determination of the characteristic helical pitch before and after the transition revealed that the transition takes place reversibly between the two α-helices having opposite screw-sense during the heating and cooling cycle. While the hexagonal packing remains unaltered, the helix-sense inversion causes discontinuous changes in the molecular arrangement and, by extension, the crystalline dimension. In this study, another transition was detected at a higher temperature from the left-handed α-helix to the π-helix, the molecular chirality being unaffected.

The Relationship between Pendant Phosphate Groups and Mechanical Properties of Polyisoprene Rubber

It is still a great challenge to mimic the structure and function of natural rubber by introducing polar components into synthetic polyisoprene. In order to explore the function of phosphate groups on the mechanical properties of polyisoprene rubber, a terminally functionalized compound (PIP-P) containing phosphate groups was synthesized and further vulcanized to prepare the model compound V-PIP-P. Through analyzing the test results, it was found that these phosphate groups formed polar aggregates in non-polar polyisoprene rubber matrix, serving as an additional dynamic cross-linking sites, which increases the cross-linking density and improves mechanical properties. The influence of the phosphate groups on the strain-induced crystallization (SIC) was further investigated via synchrotron wide-angle X-ray diffraction (WAXD) experiment. These phosphate group aggregates not only reduced the onset strain of SIC, but also slowed down the molecular chain mobility, which hinder the crystal lateral growth. The above results help us to gain a deeper understanding for the function of phosphate groups in the formation of “naturally occurring network” and guide the molecular design of next generation polyisoprene rubber.

Radiation assisted pre-oxidation of polyacrylonitrile fiber: Graphite formation and lower crystal size revealed by 2D WAXD at a synchrotron facility

To accurately understand how irradiation treatment influences the crystal structure variation of polyacrylonitrile (PAN) fibers during the pre-oxidation process, the crystal structure evolution of the irradiated PAN fibers after pre-oxidation was investigated by synchrotron wide-angle X-ray diffraction (WAXD) at beamline BL16B1 in transmission geometry, using a three-slit system at the Shanghai Synchrotron Radiation Facility. By employing highly sensitive 2D WAXD analysis, we observed the deformation of the orientation structure in the irradiated PAN fibers. It was found that irradiation treatment can reduce the quasicrystal structure formed in the early stage of the pre-oxidation process (200–220 °C). Irradiation further enhanced the decrease in crystal size, crystallinity, and preferred orientation during the pre-oxidation. The diffraction peaks for PAN fibers at q = 12 nm−1 and 20.7 nm−1 almost disappeared at 260 °C; meanwhile, a new peak appeared for the irradiated samples at q = 18.2 nm−1, indicating the formation of a graphite structure, which confirmed by Raman spectra. The results showed that irradiation treatment can accelerate the pre-oxidation reaction of PAN fiber, reduce the time required for pre-oxidation, and improve the properties of carbon fiber by reducing the crystal size and crystallinity.

A Synchrotron in situ X-ray Study on the Multiple Melting Behaviors of Isomorphous Poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (P(HB-co-HV)) with Middle HV Content

The multiple endothermic peaks without observable recrystallization phenomenon of isomorphous poly(3-hydroxybutyrate-co-3-hydroxyvalerate) [P(HB-co-HV)] with the middle HV content of 19.4 mol% and 28.7 mol% were confirmed by differential scanning calorimetry (DSC), and the evolutions of crystal structure and lamellar morphology in the heating and melting process were tracked by in situ synchrotron wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS) techniques. The emergence of asymmetric features of both the diffraction peaks and scattering curves indicates the coexistence of different lamellar crystals with varied unit cell parameters. Based on the in situ WAXD and SAXS measurements, we calculated the evolutions of the unit cell parameters a and b as well as the long period and lamellar thickness upon heating. The comparative analysis of WAXD and SAXS data confirms that the multiple endothermic peaks of P(HB-co-19.4%HV) and P(HB-co-28.7%HV) result from the melting of different lamellae rather than the melting/recrystallization. The thinner, unstable uniform lamellae with HV counits total inclusion melt first and the thicker, stable sandwich lamellae with HV counits partial inclusion melt last. In addition, the large second melting peak in P(HB-co-19.4%HV), differing from that of samples with HV content of 28.7 mol% and 36.2 mol%, is due to the unique state of HV content leading to a transition of sandwich lamellae to uniform lamellae. The present study establishes the relationship between the different lamellae structure and multiple melting behaviors of isomorphous copolymer.

Crystal polymorphism of polylactide and its composites by X-ray diffraction study

Polylactide (PLA) exhibits various types of crystal modifications depending on the preparation conditions, including the components. To solve the open question, a reliable calculation method for crystallinity, crystal forms, and composition in neat PLA and PLA composites was developed on the basis of temperature-dependent synchrotron wide-angle X-ray diffraction results. The relative composition of amorphous, α-form, and α’-form phases of PLA and its composites filled with halloysite nanotubes during heating was successfully obtained. It was found that only 47–56% of α’-form crystals transform into α-form crystals during a 2 °C/min heating process for PLA with a molecular weight of 54,300 g/mol. The loading of halloysite nanotubes decreases the cold crystallization and starting transition (α’ crystals transform into α-form crystals) temperatures of PLA. The crystallinity and the main diffraction peak intensity as a function of temperature were also analyzed. These results suggest that the α’-to-α form transition is a solid-solid phase transition. Polylactide (PLA) exhibits various types of crystal modifications depending on the preparation conditions, including the components. To solve the open question, a reliable calculation method for crystallinity, crystal forms and composition in neat PLA and PLA composites was developed on the basis of temperature-dependent synchrotron wide-angle X-ray diffraction results. The relative composition of amorphous, α-form, and α’-form phases of PLA and its composites filled with halloysite nanotubes during heating was successfully obtained.

Flow-Induced Crystallization of Crosslinked Poly(vinylidene fluoride) at Elevated Temperatures: Formation and Evolution of the Electroactive β-Phase

Flow-induced crystallization of poly(vinylidene fluoride) (PVDF) was investigated for a broad temperature range from 160 to 220 °C by in situ synchrotron wide-angle X-ray diffraction (WAXD) and sma...

Probing the structural evolution in deformed isoprene rubber by in situ synchrotron X-ray diffraction and atomic force microscopy

Developing a better understanding of the structural evolution in deformed polymers is key to designing new materials and structures that achieve superior mechanical properties. Here, we used in situ synchrotron wide-angle X-ray diffraction (WAXD) and atomic force microscopy (AFM) nanomechanical mapping (AFM-NM) to assess the strain-induced crystallization (SIC) and the associated structural evolution and mechanical properties of peroxide vulcanized isoprene rubber (IR) as a function of crosslink density (ν) and strain. The WAXD and AFM-NM results show agreement in the onset strain of SIC. Crystalline reflections appears in the WAXD while a nanofibrillar structure is found by AFM-NM. The higher ν, the smaller is the onset strain of a steep upturn in the stress-strain curves, the smaller is the onset strain of SIC, the higher is the crystallinity as evidenced in the WAXD, and the larger is the amount of nanofibrils seen by AFM-NM. Both WAXD and AFM-NM results show the SIC occurs rapidly at high strains while most chains remain in the amorphous state. The elastic modulus of the formed nanofibrils that range in diameter from several to a hundred nanometers, is two times higher than that of the amorphous regions. From the WAXD and AFM-NM results, a schematic model of structural evolution is proposed and used to illustrate the self-reinforcement mechanism in IR.

Structural evolution of stretch deformed HDPE/RGO nanocomposites: An in-situ synchrotron SAXS and WAXD study

We have reported that the incorporation of reduced graphene oxide (RGO) can induce epitaxial crystallization of high density polyethylene (HDPE) on RGO surfaces and then enhance mechanical properties of HDPE/RGO nanocomposites, but the underline intensifying mechanism remains unclear. Herein, to further unveil the influence of epitaxial crystallization imposing on the improvement of mechanical properties, the structural evolution of HDPE/RGO nanocomposites during the stretching process is explored as a function of RGO content by in-situ synchrotron wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS) techniques. It has shown that the introducing of RGO apparently retards the structural evolution in the tensile deformation and the hysteresis is accentuated dramatically with increasing RGO content. The epitaxial growth of HDPE upon RGO surfaces forms large sized crystals and the amount of epitaxial crystals enlarges with RGO content. The coupling of the remained existence of large sized crystals and the smaller density after stretching demonstrates that the interplay between RGO and large amount of epitaxial crystals can undergo the strong stress and thus hampers and delays the structure change and crystal fragmentation during the tensile deformation of HDPE/RGO nanocomposites. The present results not only makes clear that it is the epitaxial crystallization stemming from interfacial interaction between HDPE and RGO that plays the major role to delay the structural evolution and damage and thus lead to the enhancement of mechanical properties of HDPE/RGO nanocomposites, but reveal the underline stress-induced fragmentation-recrystallization mechanism for this tensile deformation.

Interfacial Stereocomplexation To Strengthen Fused Deposition Modeled Poly(lactide) Welds

The interlayer stiffness of fused deposition modeled (FDM) parts is significantly impaired by the slow diffusion and re-entangling of polymer chains across filament interfacial welds in the build direction. To mechanically reinforce FDM interfaces, an approach based on timing and spatial direction of stereocomplexation across weld interfaces is introduced via alternating deposition of enantiomerically opposite poly(lactides). Fundamental insight into the kinetics and spatial distribution of homo- and stereocrystallization at FDM interfaces was successfully reconstructed in 2 and 3 dimensions by micrometer resolved Fourier transform infrared microscopy and synchrotron wide-angle X-ray diffraction tomography. The rate of isothermal stereocomplexation and consequential interfacial stiffening increases with decreased absolute and relative molar masses. The spatial distribution of stereocrystals is governed by the relative molar masses and the extent of interdiffusion, under not only isothermal but also nonisothermal FDM conditions. The net local heat dosage, which depends on print speed, governs the length scales of stereocomplexation and thus mechanical reinforcement. Interfacial stereocomplexation of poly(lactides) in FDM leads to a distinct 40% increase in stiffness and nucleation of bulk filaments, aiding in thermodynamic and geometrical stability.