RESUMO
This study introduces a novel method that utilizes evolved gas analysis with time-of-flight mass spectrometry (EGA-TOFMS) coupled with principal component analysis (PCA) and Kendrick mass defect (KMD) analysis, called EGA-PCA-KMD, to analyze complex structural changes in polymer materials during thermo-oxidative degradation. While EGA-TOFMS captures exact mass data related to the degradation components in the temperature-dependent mass spectra of the evolved products, numerous high-resolution mass spectra with large amounts of ion signals and varying intensities provide challenges for interpretation. To address this, we employed mathematical decomposition through PCA to selectively extract information about the ion series specific to the products that evolved from the degradation components. Additionally, KMD analysis was applied to the attribution of the exact mass signals extracted from the PCA, which categorizes and visualizes depending on the molecular compositions in a two-dimensional plot. The complex structural changes of the triblock copolymer thermoplastic elastomer and its nanocomposites containing nanodiamonds during thermo-oxidative degradation were elucidated using EGA-PCA-KMD to demonstrate the effectiveness of this characterization technique for polymer degradation. Furthermore, it is revealed that the formation of rigid matrix-filler interfacial interaction via the π-π stacking and chemical bonds in the nanocomposites contributes to improvement in the stability toward thermo-oxidative degradation. Our results highlight the benefits of EGA-PCA-KMD and provide valuable insights into polymer degradation.
RESUMO
We have developed a novel rheo-optical Fourier-transform infrared (FTIR) imaging technique that can probe the molecular-scale deformation behavior of a polymer matrix in composite materials. This rheo-optical FTIR imaging is based on in situ-polarized FTIR imaging of a polymer sample while it is being deformed by mechanical force. This imaging technique readily captures the orientation of the polymer molecules resulting from the applied strain. Analysis of the resulting FTIR imaging data by disrelation mapping makes it possible to further elucidate subtle but pertinent spectral variations arising from changes in the state of molecules within the spectroscopic images. In this study, the rheo-optical FTIR imaging is applied to analysis of the deformation behaviors of a composite composed of polypropylene containing hydroxyl groups (PPOH) and silica spheres (SS) to investigate matrix-filler adhesion of the composite. Our rheo-optical FTIR imaging analysis revealed selective inhibition of PPOH orientation at the matrix-filler interface during tensile deformation due to high matrix-filler adhesion via hydrogen bonding. The strong link between the PPOH matrix and SS filler efficiently restricts mobility of the matrix, resulting in the reinforcement of PPOH by addition of SS. Rheo-optical FTIR imaging is an effective tool for probing localized deformation behavior at the matrix-filler interface as well as achieving a better understanding of the correlation between matrix-filler adhesion and the effective reinforcement of composites.
RESUMO
A simple and effective strategy for improving the accuracy of the multivariate determination of polyethylene (PE) density using Raman spectroscopy has been demonstrated. This strategy is based on the possibility that varied polymeric structures of the PE samples, especially at a sub-zero temperature range, would enhance their spectral selectivity, thereby potentially improving the multivariate correlation with their pre-determined physical properties such as density. For the evaluation, Raman spectra were collected at regular intervals during continuous increase of the PE temperature from cryogenic to near room temperature. Then, using partial least squares (PLS) regression, calibration models were developed to correlate the Raman spectral features collected at each time period with the reference PE density values. Interestingly, the accuracy was improved when the temperature of the PE pellets was -35 °C, near the glass transition temperature (Tg). To explain the improved accuracy, a two-dimensional (2D) correlation analysis was employed to detail the spectral variation induced by temperature change. Diverse segmental chain motions (so called micro-Brownian motion) predominantly occurring in the amorphous section of the PEs around Tg greatly enhanced the spectral selectivity among PE samples. In addition, minor ß-relaxation occurring around this temperature was an additional source of the enhanced spectral selectivity. In parallel, differential scanning calorimetry (DSC) curves of the samples were also examined to check the existence of the phase transitions.
RESUMO
The crystal structures of active pharmaceutical ingredients and excipients should be strictly controlled because they influence pharmaceutical properties of products which cause the change in the quality or the bioavailability of the products. In this study, we investigated the effects of microcrystalline cellulose (MCC) crystallinity on the hydrophilic properties of tablets and the hydrolysis of active pharmaceutical ingredient, acetylsalicylic acid (ASA), inside tablets by using tablets containing 20% MCC as an excipient. Different levels of grinding were applied to MCC prior to tablet formulation, to intentionally cause structural variation in the MCC. The water penetration and moisture absorbability of the tablets increased with decreasing the crystallinity of MCC through higher level of grinding. More importantly, the hydrolysis of ASA inside tablets was also accelerated. These results indicate that the crystallinity of MCC has crucial effects on the pharmaceutical properties of tablets even when the tablets contain a relatively small amount of MCC. Therefore, controlling the crystal structure of excipients is important for controlling product qualities.
Assuntos
Aspirina/química , Celulose/química , Preparações Farmacêuticas/química , Comprimidos , Cristalização , Excipientes , Hidrólise , Interações Hidrofóbicas e Hidrofílicas , Tomografia Computadorizada por Raios XRESUMO
In this study, a new system was developed to carry out simultaneous near-infrared (NIR) and small-angle X-ray scattering (SAXS) measurements. Aged PP was examined with the NIR-SAXS system to demonstrate how it can be utilized to derive pertinent information about polymer structure. Pairs of SAXS profiles and NIR spectra of PP in its initial state and after aging were measured to derive an in-depth understanding of the aging phenomenon. The SAXS profiles of the PP samples showed a clear shift of the SAXS peak to the lower q direction induced by the thermal aging, indicating an increase in the length of the long-period structure. Two-trace two-dimensional (2T2D) asynchronous correlation spectra derived from NIR spectra clearly revealed that the aging treatment leads to the substantial increase in the spectral intensity of the regularity bands representing the longer helix present in a folded lamellar structure. In other words, it suggest that the long helix structure is more abundantly present than the short helix structure in the aged PP than in the initial PP. By combining the information derived from the SAXS profiles and NIR spectra, the details of the aging-induced variation were clearly determined. Namely, aging causes additional crystallization of the PP by developing more helix structures, which involves an increase in lamellar thickness as well as a decrease in the amorphous region. The growth of the rigid crystalline phase restricts the elastic deformation in the amorphous structure, which eventually induces the deterioration of PP by making the polymer hard but brittle. Such observation, in turn, implies that the retarding or accelerating the crystallized structure of PP substantially works to control the progress of the aging.
RESUMO
A rheo-optical characterization technique based on the combination of near-infrared (NIR) spectroscopy and tensile testing was applied for the first time to an actual rubber sample based on styrene-butadiene rubber (SBR) including silica filler. When SBR samples were subjected to mechanical deformation, changes in the NIR spectral features were readily captured. Two-trace two-dimensional (2T2D) correlation analysis was then applied to the sets of NIR spectra to clearly reveal the subtle but pertinent difference between the NIR spectral features of the initial and deformed SBR. The initial deformation of the sample induces greater deformation of the soft butadiene groups than of the hard styrene groups. The inclusion of the silica filler and a coupling agent (CA) essentially develops firm links between the silica and butadiene via the CA to restrict the displacement of the butadiene during the tensile deformation of the system. The development of such linkage requires even more mechanical force to deform the SBR, which, in turn, improves Young's modulus of the rubber system. Asynchronous correlation spectra of SBR with no silica filler revealed that, during the deformation of the SBR, the butadiene groups were initially deformed, and this feature was then replaced by the predominant deformation of the hard styrene groups. On the other hand, this correlation feature became somewhat unclear when a similar analysis was applied to the SBR sample with silica filler, revealing subtle differences in interaction between individual comonomer functional groups distributed randomly along the copolymer chain and CA.
RESUMO
The parallel factor (PARAFAC) kernel matrix to analyze a sample system stimulated by more than one type of perturbation is described. PARAFAC kernel is a quantitative representation of the synchronicity and asynchronicity observed within the PARAFAC score matrices generated by carrying out two-dimensional (2D) correlation analyses. Thus, kernel matrix representation provides more intuitively understandable interpretation to the conventional PARAFAC trilinear model. In this study, the utility of PARAFAC kernel is demonstrated by the study of poly(lactic acid)-nanocomposite undergoing a structural change depending on the temperature as well as the clay content in the sample. Seemingly complicated variation of nuclear magnetic resonance (NMR) spectra induced by the change in the temperature and clay content are readily analyzed by the multiple-perturbation 2D correlation spectroscopy and PARAFAC kernel. PARAFAC kernel revealed that crystalline and amorphous structures of the PLA substantially undergo thermal deformation, and these variations are also influenced by the presence of the clay.
RESUMO
An optical coherence tomography (OCT) system combined with near-infrared spectroscopy (NIRS) was developed to carry out simultaneously the cross-sectional observation and spectral measurement of a specific area inside a polymer sample. This OCT-NIRS system consists of a fiber-optic-based spectrometer combined with an OCT system and enables non-invasive imaging up to a depth of several millimeters and the recording of the NIR spectrum in the observed area. A subsequent analysis of the collected data will provide key information revealing the way in which the microscopic structure of the polymer is affected by the chemical composition around it. A structural defect inside a molded polyamide (PA) 66 sample was examined with the OCT-NIRS system to demonstrate how this technique can be utilized to characterize chemical composition as well as the morphological features inside the sample. A specific void was detected by OCT when the PA sample was molded without any drying treatment. The NIR spectrum collected around the void area of the undried PA was then compared with that of vacuum-dried PA by two-trace two-dimensional (2T2D) correlation analysis to identify a subtle but pertinent difference in the spectral features. The appearance of several correlation peaks in the 2T2D asynchronous correlation spectrum revealed that the OH group represented by the NIR band at 1446 nm is found in relative abundance around the void, which clearly reveals that the development of the void in the molded PA results from inadequate sample pretreatment.
Assuntos
Nylons , Tomografia de Coerência Óptica , Estudos Transversais , Espectroscopia de Luz Próxima ao Infravermelho/métodos , Tomografia de Coerência Óptica/métodosRESUMO
Disrelation mapping was applied to Raman imaging data for the first time to investigate submolecular-level variations that occurred at the interface between glass fiber (GF) and polypropylene (PP). Disrelation maps constructed with Raman spectra provided spatial as well as spectral information, which are not readily accessible from hypercubic data. For example, patterns that appeared in the disrelation maps showed the predominant development of a long helix band (1002 cm-1) at the interface between the GF and PP, rather than a short helix band (974 cm-1). The development of the disrelation intensity was observed inside the sample as well as at the surface. These results clearly reveal that the GF or compatibilizer works intrinsically as a nucleating agent to induce additional development of the crystalline structure of the PP, which eventually makes the polymer system harder but more brittle.
RESUMO
Nanodiamond/polyamide (ND/PA) nanocomposite was examined with infrared (IR) microscopy and time-domain nuclear magnetic resonance (TD-NMR) to elucidate in detail the interphase between amino functionalized ND (ND-NH2) and PA 66. An IR image of the ND/PA nanocomposite suggested the uniform nanoscale distribution of the ND-NH2 particles thanks to the spherical shape and accessible external surface of ND terminated with reactive amino groups. On the other hand, a substantial level of change was observed in T2 decay curves when the ND-NH2 particles were incorporated in the PA 66. The fine features of the thermally induced changes in the decay curves were readily analyzed with the two-trace two-dimensional (2T2D) correlation method. The variation in the asynchronous correlation intensity indicated that the changes observed in the mechanical properties of the ND/NH2 may be attributed to the development of crosslinking between tie chains in the amorphous region via the interaction between the ND-NH2 and PA 66. Accordingly, such firm links have a substantial effect in preventing the displacement of the amorphous domain, which eventually increases the Young's modulus but reduces the ductility of the PA.
RESUMO
A novel strategy is demonstrated to improve the accuracy for determination of polyethylene (PE) density using Raman spectroscopy by optimizing the temperature of sample measurement. Spectral features associated with the conformation change of the polymer induced by temperature may provide valuable information to quantify important polymer properties such as density. To evaluate possible existence of an optimal temperature providing improved quantitative accuracy, Raman spectra of PE pellets with different densities were collected at eight different temperatures from 30 to 100 °C at 10 °C intervals. Using the spectral datasets collected at each temperature, partial least squares (PLS) models were developed using the reference PE density values determined by a standard density gradient method at 23 °C. Interestingly, the most accurate determination of density was realized at 70 °C. Multiple perturbation two-dimensional (MP2D) correlation analysis and differential scanning calorimetry (DSC) were used to examine the origin of improved accuracy at 70 °C. From these analyses, the pre-melt behavior of the PE samples was identified below their melting temperatures. Structural variations induced at the pre-melt stages enhance Raman spectral selectivity among the samples, thereby providing more accurate determination of PE density. The MP2D correlation analysis revealed the unforeseen thermal behavior of PE samples and successfully explained the improved accuracy at 70 °C.
RESUMO
A binary amorphous polymer blend consisting of polyvinyl chloride (PVC) and polymethyl methacrylate (PMMA) was studied with a rheo-optical characterization technique based on the combination of a near-infrared (NIR) spectrometer and a tensile testing machine. In rheo-optical NIR spectroscopy, tensile deformations were applied to polymers to induce the displacement of molecular chains while being probed by NIR light. The application of this technique was extended to a partially miscible amorphous polymer blend consisting of PVC and PMMA to demonstrate how it can be utilized to detect subtle but important deformation behavior. A change in the NIR spectral feature revealed that the initial deformation of the blend induces the reorientation of the PVC chains. A part of the PMMA connected to the PVC was tagged during the PVC deformation. Further deformation of the sample eventually resulted in necking propagation to the surrounding area.
RESUMO
Exposing polymers to high-pressure and supercritical CO2 is a useful approach in polymer processing. Consequently, the mechanisms of polymer-polymer interaction under such conditions are worthy of further investigation. Two-dimensional correlation analysis and two-dimensional disrelation mapping were applied to datasets of polycaprolactone -poly(lactic acid) blend with or without high-pressure CO2 obtained using in situ attenuated total reflection Fourier transform spectroscopic imaging. The relatively weak dipole-dipole intermolecular interactions between polymer molecules were visualized through the disrelation maps for the first time. Because of the specially designed polymer interface, the interactions between the same type of polymer molecules and different types of polymer molecules were differentiated. Under exposure to high-pressure CO2, all three types of interactions: interaction between polycaprolactone molecules and poly(lactic acid) molecules, interaction between polycaprolactone molecules and interaction between poly(lactic acid) molecules become weaker than those in the polymer interface without high-pressure CO2. The resulting increase in the Flory interaction parameter is the main cause of phase separation in the PCL-PLA blend under high-pressure CO2. The findings from this study will be of benefit for polymer processing with high-pressure and supercritical CO2.
RESUMO
A technique for analyzing infrared imaging data based on two-trace two-dimensional (2T2D) correlation analysis is presented to extract pertinent information underlying spectroscopic imaging data. In 2T2D correlation mapping, each spectrum in hyperspectral data is individually compared with a reference spectrum to generate 2T2D asynchronous correlation intensity at the x- and y-coordinates on a 2T2D correlation map. Asynchronous correlation intensity develops only when the signal contribution from a certain species becomes even more significant in the sample spectrum compared with the reference spectrum. This feature can be advantageously utilized to examine molecular interaction or an intermediate form of the component present in a system of interest. 2T2D correlation mapping is examined using Fourier transform infrared imaging data of polymer composites based on polypropylene grafted with maleic anhydride melt-mixed with silica spheres. Infrared images derived by using conventional visualization based on a single wavenumber (i.e., 1713 cm-1) are dominated with the overwhelming infrared absorbance induced by the normal maleic anhydride species, making the identification of subtle but pertinent changes in the composite system difficult. A 2T2D correlation map derived from the maleic anhydride/silica spheres composite developed a significant asynchronous correlation intensity between the infrared bands at 1695 and 1713 cm-1 around a specific region on the map where the maleic anhydride and silica spheres coexist. On the other hand, such a correlation pattern becomes less acute when the silica spheres is modified with the octadecyldimethyl group to prevent the hydrogen bonding with the maleic anhydride. It thus revealed that the silanol groups on the surface of the silica spheres substantially interact with the maleic anhydride via the development of the hydrogen bonding.
RESUMO
An extension of the two-dimensional (2D) correlation analysis scheme for multi-dimensional perturbation is described. A simple computational form is provided to construct synchronous correlation and disrelation maps for the analysis of microscopic imaging data based on two independent perturbation variables. Sets of time-dependent attenuated total reflection infrared (ATR-IR) spectra of water and cellulose mixtures were collected during the evaporation of water from finely ground cellulose. The system exhibits complex behaviors in response to two independent perturbations, i.e., evaporation time and grinding time. Multiple perturbation 2D analysis reveals a specific difference in the rate of evaporation of water molecules when accompanied by crystallinity changes of cellulose. It identifies subtle differences in the volatility of water, which is related to the crystalline structure of cellulose.
Assuntos
Celulose/análise , Espectrofotometria Infravermelho/métodos , Água/química , Celulose/química , Volatilização , Difração de Raios XRESUMO
A rheo-optical characterization technique based on the combination of near-infrared (NIR) spectroscopy and mechanical analysis was applied to the nanocomposite consisting of hydroxyl-functionalized polypropylene (PPOH) and mesoporous silica (MPS) to probe the deformation behavior. Substantial levels of spectral changes of NIR spectral features were captured when the polymer samples underwent tensile deformation. Sets of spectra were subjected to projection treatment to remove the effect of baseline fluctuations and thickness change inevitably caused by the tensile deformation of the sample. Then, two-trace two-dimensional (2T2D) correlation spectroscopy was applied to the pretreated spectra to elucidate spectroscopic signature associated with the difference between the initial and deformed samples. An asynchronous correlation peak appears between the bands at 1720 and 1700 nm respectively reflecting the contributions of predominantly amorphous and crystalline component of the PPOH, indicating the predominant variation of amorphous structure followed by that of crystalline structure. In addition, the predominant spectral change related to the amorphous band becomes even more acute by including the MPS with large pores. It is hence likely that the larger pore size of the MPS confines the more amorphous structure, which, in turn, causes simultaneous reorientation of the polymer chains in the amorphous region during the elastic deformation. Consequently, the incorporation of the MPS selectively restricts the deformation of the amorphous structure which eventually provides the obvious increase in the mechanical property of the PPOH polymer.
RESUMO
Sensitive detection of near-infrared (NIR) spectra of several organic liquids has been carried out by surface plasmon resonance (SPR) NIR spectroscopy. For all the liquids, 50- to 100-fold enhancements of the absorption peaks were obtained in the combination band region 4500-4000 cm(-1) using a gold film with a thickness of 14 nm. The SPR peak shows up as an unnecessary broadband peak or trend in an SPR-NIR spectrum, and it was difficult to separate it from the absorption signals. In order to remove the contribution of SPR from the raw SPR-NIR spectrum, the second-order derivative has been employed. The second derivative of the SPR-NIR spectrum was reasonably comparable to that of the corresponding transmittance spectrum. Two simple algorithms for sample identification from the second-derivative data have been proposed. One is similarity, which directly compares the second-derivative spectrum of an unknown sample with that of a known reference sample. The other is fitness, which is defined as a ratio of the common part of absorption peak wavenumbers of the sample and the reference. Although both methods are unfit for the identification of a minor component in a mixture, a major component can be definitely identified by choosing an informative wavenumber region. It was found that the wavenumber region 4250-4080 cm(-1) is especially useful for the identification of similar molecules such as normal alkanes.
RESUMO
Tensile deformations of a partially miscible blend of polymethyl methacrylate (PMMA) and polyethylene glycol (PEG) is studied by a rheo-optical characterization near-infrared (NIR) technique to probe deformation behavior during tensile deformation. Sets of NIR spectra of the polymer samples were collected by using an acousto-optic tunable filter (AOTF) NIR spectrometer coupled with a tensile testing machine as an excitation device. While deformations of the samples were readily captured as strain-dependent NIR spectra, the entire feature of the spectra was overwhelmed with the baseline fluctuation induced by the decrease in the sample thickness and subsequent change in the light scattering. Several pretreatment techniques, including multiplicative scatter collection (MSC) and null-space projection, are subjected to the NIR spectra prior to the determination of the sequential order of the spectral intensity changes by two-dimensional (2D) correlation analysis. The comparison of the MSC and null-space projection provided an interesting insight into the system, especially deformation-induced variation of light scattering observed during the tensile testing of the polymer sample. In addition, the sequential order determined with the 2D correlation spectra revealed that orientation of a specific part of PMMA chain occurs before that of the others because of the interaction between CO group of PMMA and terminal OH group of PEG.
RESUMO
Hydrogen/deuterium (H/D) exchange of gelatinized starch was probed by in-situ near-infrared (NIR) monitoring coupled with two-dimensional (2D) correlation spectroscopy. Gelatinized starch undergoes spontaneous H/D exchange in D2O. During the substitution, the exchange rate essentially becomes different depending on solvent accessibility of various parts of the molecule. Thus, by analyzing the change in the NIR feature observed during the substitution, it becomes possible to sort out local structure and dynamics of the system. 2D correlation analysis of the time-dependent NIR spectra reveals the presence of different local structure of the starch, each having different solvent accessibility. For example, during the H/D exchange, the D2O is first absorbed by starch molecules especially around the surface area between the starch and water, where the water molecules are weakly interacted with the starch molecules. This absorption is quickly followed by the development of HDO species. Further absorption of the D2O results in the penetration of the molecules inside the starch and eventually develops the relatively strong interaction between the HDO and starch molecules because of the presence of dominant starch molecules.
RESUMO
Data presented here are related to the original paper "Concentration determination of inorganic acids that do not absorb near-infrared (NIR) radiation through recognizing perturbed NIR water bands by them and investigation of accuracy dependency on their acidities" published by same authors. Here, the concentration-dependent score variations and the results of 2D correlation analysis in the measurements of H2SO4, HNO3, and H3PO4 samples are included; while, the same analysis results obtained in the measurement of HCl samples are presented in the main manuscript. In addition, the correlation plots resulted in the measurements of HCl, H2SO4, HNO3, and H3PO4 samples are also separately shown.