Search Results (20)

Ensuring thermal stability is a major concern in lithium-ion battery systems. Although phase change materials (PCMs) provide a passive approach for temperature regulation, they are limited by poor heat conduction and potential leakage during phase transitions. This study develops a novel composite PCM (CPCM) using paraffin (PA) as the matrix, copper foam (CF) as a conductive skeleton (10–30 pores per inch, PPI), and a low-melting-point alloy (LMA) as an encapsulant to prevent leakage. The effects of CF pore size on thermal conductivity, impregnation ratio, and leakage resistance were systematically investigated. Results show that CPCM with 10 PPI CF achieved the highest thermal conductivity (4.42 W·m⁻¹·K⁻¹), while LMA encapsulation effectively eliminated leakage. The thermal management performance was evaluated on both a single 18,650 LIB cell and a 2S2P module during rate discharging at 1C, 2C, and 3C. For the module at 3C, the 10 PPI CPCM significantly lowered the maximum temperature from 75.9 °C to 44.6 °C and critically reduced the maximum temperature difference between cells from 10.2 °C to a safe level of 1.2 °C, significantly improving temperature uniformity. This work provides a high-conductivity and leakage-proof CPCM solution based on LMA-encapsulated CF/PA for enhanced thermal safety and uniformity in LIB modules. Full article

In this paper, we present the analysis of functional alloy samples containing metals aluminum (Al), copper (Cu), lead (Pb), silicon (Si), tin (Sn), and zinc (Zn) using a Q-switched Nd laser operating at a wavelength of 532 nm with a pulse duration of 5 ns. Nine pelletized alloy samples were prepared, each containing varying chemical concentrations (wt.%) of Al, Cu, Pb, Si, Sn, and Zn—elements commonly used in electrotechnical and thermal functional materials. The laser beam is focused on the target surface, and the resulting emission spectrum is captured within the temperature interval of $9.0\times {10}^3$ to $1.1\times {10}^4$ K using a set of compact Avantes spectrometers. Each spectrometer is equipped with a linear charged-coupled device (CCD) array set at a 2 μs gate delay for spectrum recording. The quantitative analysis was performed using calibration-free laser-induced breakdown spectroscopy (CF-LIBS) under the assumptions of optically thin plasma and self-absorption-free conditions, as well as local thermodynamic equilibrium (LTE). The net normalized integrated intensities of the selected emission lines were utilized for the analysis. The intensities were normalized by dividing the net integrated intensity of each line by that of the aluminum emission line (Al II) at 281.62 nm. The results obtained using CF-LIBS were compared with those from the laser ablation time-of-flight mass spectrometer (LA-TOF-MS), showing good agreement between the two techniques. Furthermore, a random forest technique (RFT) was employed using LIBS spectral data for sample classification. The RFT technique achieves the highest accuracy of ~98.89% using out-of-bag (OOB) estimation for grouping, while a 10-fold cross-validation technique, implemented for comparison, yields a mean accuracy of ~99.12%. The integrated use of LIBS, LA-TOF-MS, and machine learning (e.g., RFT) enables fast, preparation-free analysis and classification of functional metallic materials, highlighting the synergy between quantitative techniques and data-driven methods. Full article

The potential of using laser-induced breakdown spectroscopy (LIBS) in combination with various other spectroscopic and statistical methods was assessed for characterizing pure and MgO-doped nylon (6/6) organic polymer samples. The pure samples, obtained through a polycondensation chemical technique, were artificially doped with MgO prior to analysis for comparative purposes. These artificially doped samples served as crucial reference materials for comparative analysis and reference purposes. The LIBS studies were performed under local thermodynamic equilibrium (LTE) and optically thin plasma conditions. To assess the structural crystallinity of the nylon (6/6) polymer samples, X-ray diffraction (XRD) analysis, and Fourier transform infrared (FTIR) spectroscopy were employed to detect functional groups such as N-H, C-H, and C-N in the adsorbent polyamide nylon sample. Additionally, diffuse reflectance spectroscopy (DRS) analysis was conducted to investigate the effects of doping and temperature on the band gap and material reflectance across different sample temperatures. Chemical compositional analysis was performed using X-ray photoelectron spectroscopy (XPS) with the carbon C1s peak at 248.8 eV serving as a reference for spectrum calibration, along with energy-dispersive X-ray (EDX) analysis, which demonstrated good agreement between the techniques. To validate the different methodologies, the results obtained from CF-LIBS and EDX were compared with those from the standard inductively coupled plasma mass spectrometry (ICP-MS) technique. Finally, for classification analysis, principal component analysis (PCA) was applied to the LIBS spectral data at different sample temperatures (25 °C, 125 °C, 225 °C, and 325 °C). The analyses demonstrated that the combination of LIBS with PCA, along with other methods, presents a robust technique for polymer characterization. Full article

In this present work, we demonstrated a spectral characterization of copper–iron (Cu-Fe) alloy using optical emission spectroscopy. The Cu-Fe alloy plasma was generated on the target sample surface by directing the laser pulse of Q-switched Nd: YAG of the second harmonic (2ω) with a 532 nm optical wavelength. The optical emission spectrum was acquired using five miniature spectrometers that lie within the wavelength range of 200–720 nm. The emission plasma was characterized by validating the local-thermodynamical equilibrium (LTE) as well as optically thin (OT) plasma condition. In addition, the LTE condition was verified using the McWhirter criterion, and the OT condition was validated by comparing theoretically calculated intensity ratios with experimental ones. Plasma parameters, including electron number density as well as plasma temperature, were estimated. In the first stage, the plasma temperature was estimated using the Boltzmann-plot method and the two-line method. The average calculated value of the plasma temperatures were 8014 ± 800 K and 8044 ± 800 K using the Boltzmann-plot and two-line methods, respectively. In the second stage, electron number density was estimated using the Saha–Boltzmann equation and stark-broadening method (SBM). The average number density calculated from the SBM was $2.73\times {10}^{16} {\mathrm{cm}}^{-3}$ and from the Saha–Boltzmann equation was $3.9\times {10}^{16} {\mathrm{cm}}^{-3}$, showing a good agreement. Finally, the comparative compositional analysis was performed using CF-LIBS, Boltzmann Intercept Method, EDX, and ICP-AES, which showed good agreement with that of the standard composition. Full article

Rare earth elements are gaining significant importance in the scientific and technological fields for their exciting physical properties and characteristics. The aim of the present study was to determine rare earth elements (REEs) in geological ores found in the Northern Areas of Pakistan. We present the application of laser-induced breakdown spectroscopy (LIBS) and laser ablation time-of-flight mass spectrometry (LA-TOF-MS) for the elemental analysis of geological ore samples containing REEs. The laser-induced plasma plume exhibits a wide array of emission lines, including those of rare earth elements such as Ce, La, and Nd. Furthermore, the spectral range, from 220 nm to 970 nm, encompasses emission lines from C, Fe, Ti, Na, Mg, Si, and Ca. The qualitative analysis of the constituent elements in the samples was performed by comparing the LIBS spectrum of the unknown sample with that of the spectroscopically pure rare earth elements (La₂O₃, CeO₂, and Nd₂O₃, with 99.9% metals basis) recorded under the same experimental conditions. The quantitative analysis was performed using the calibration-free laser-induced breakdown spectroscopy (CF-LIBS), LA-TOF-MS, and energy-dispersive X-ray (EDX) techniques. The results obtained by CF-LIBS were found to be in good agreement with those obtained using the LA-TOF-MS and EDX analytical techniques. LIBS is demonstrated to yield a quick and reliable qualitative and quantitative analysis, of any unknown geological sample, comparable to that of the other analytical techniques. Full article

In this study, multi-walled carbon nanotubes (MWCNTs) were modified by thermal fluorination to improve dispersibility between MWCNTs and Li₄Ti₅O₁₂ (LTO) and were used as additives to compensate for the disadvantages of LTO anode materials with low electronic conductivity. The degree of fluorination of the MWCNTs was controlled by modifying the reaction time at constant fluorination temperature; the clear structure and surface functional group changes in the MWCNTs due to the degree of fluorination were determined. In addition, the homogeneous dispersion in the LTO was improved due to the strong electronegativity of fluorine. The F-MWCNT conductive additive was shown to exhibit an excellent electrochemical performance as an anode for lithium ion batteries (LIBs). In particular, the optimized LTO with added fluorinated MWCNTs not only exhibited a high specific capacity of 104.8 mAh g⁻¹ at 15.0 C but also maintained a capacity of ~116.8 mAh g⁻¹ at a high rate of 10.0 C, showing a capacity almost 1.4 times higher than that of LTO with the addition of pristine MWCNTs and an improvement in the electrical conductivity. These results can be ascribed to the fact that the semi-ionic C–F bond of the fluorinated MWCNTs reacts with the Li metal during the charge/discharge process to form LiF, and the fluorinated MWCNTs are converted into MWCNTs to increase the conductivity due to the bridge effect of the conductive additive, carbon black, with LTO. Full article

In the present work, the rapid identification of elements and their relative chemical composition in various Peganum harmala seed samples were investigated using a calibration-free laser-induced breakdown spectroscopy technique (CF-LIBS). A pulsed Nd:YAG laser-source with a 5 ns pulse-duration, and 10 Hz pulse repetition rates providing 400 and 200 mJ energy at 1064 and 532 nm wavelength, respectively, was focused on the Peganum harmala seed samples for ablation. A LIBS 2000+ spectrometer within the wavelength range (200 to 720 nm), emission-spectra were recorded. The measured spectra of the Peganum harmala sample gives spectral lines of Carbon (C), Magnesium (Mg), Lithium (Li), Sodium (Na), Calcium (Ca), Silicon (Si), Iron (Fe), Strontium (Sr), Copper (Cu), Potassium (K), and Lead (Pb). A CF-LIBS technique has been employed for the compositional study of the elements exist in the Peganum harmala seed samples. The measured results demonstrate that C, Mg, and Ca are found to be major elements in the Peganum harmala seed samples with compositions of ~36.64%, ~24.09%, and ~19.03%, respectively. Along with the major elements, the elements including Li, Na, Si, K, Fe, and Sr were identified as minor elements with compositions of ~2.87%, ~2.33%, ~3.72%, ~7.17%, ~2.83%, and ~1.14%, respectively. Besides Cu (~8.07 μg/g), and Pb (~1.10 μg/g) elements were observed as trace elements exist in the Peganum harmala seed samples. Furthermore, the electron number density including the plasma excitation-temperature were calculated using the stark-broadening line profile method and the Saha–Boltzmann plot method, respectively. The plasma parameters versus laser-irradiance and the distance from the sample were further investigated. Moreover, a principal component analysis (PCA) method was also utilized to the spectral data obtained by using LIBS to discriminate various seed samples with four classes, namely, α, β, γ, and Δ. Three principal-components (PCs) calculated from eigenvalues of score matrix described 87.6%, 4.6%, and 2.5% of total variance for PC1, PC2, and PC3, respectively. The LIBS spectral data variance covered by the initial 3 PCS was found as ~94.7% of total variance. The PCA results have successfully demonstrated the different classes of the Peganum harmala seed samples based on the different doping compositional ratios of the Zn element. This study confirmed the feasibility and ability of LIBS and PCA for the rapid analysis of Peganum harmala seed samples. Finally, the results achieved using CF-LIBS were incorporated with those obtained from the XRF and EDX analytical techniques. Full article

In this work we report the characterization of thin metallic coatings of interest for nuclear fusion technology through the ns double-pulse LIBS technique. The coatings, composed of a tungsten (W) or tungsten-tantalum (W-Ta) mixture were enriched with deuterium (D), to simulate plasma-facing materials (PFMs) or components (PFCs) of the next generation devices contaminated with nuclear fuel in the divertor area of the vacuum vessel (VV), with special attention to ITER, whose divertor will be made of W. The double pulse LIBS technique allowed for the detection of D and Ta at low concentrations, with a single laser shot and an average ablation rate of about 110 nm. The calibration free (CF-LIBS) procedure provided a semi-quantitative estimation of the retained deuterium in the coatings, without the need of reference samples. The presented results demonstrate that LIBS is an eligible diagnostic tool to characterize PFCs with high sensitivity and accuracy, being minimally destructive on the samples, without PFCs manipulation. The CF-LIBS procedure can be used for the search for any other materials in the VV without any preliminary reference samples. Full article

The present manuscript explores a spectroscopic technique to select turmeric powder, free from impurities, and has compounds of medicinal importance among the tainted and natural turmeric. Six Curcuma longa (turmeric powder) samples, named S1, S2, S3, S4, S5, and S6, were analyzed to discriminate between tainted and natural turmeric using the LIBS and multivariate technique. Other techniques such as UV–Vis, FTIR, and EDX are also used to ascertain the elements/compounds showing the medicinal properties of C. longa. Spectral lines of carbon, sodium, potassium, magnesium, calcium, iron, strontium, barium, and electronic bands of CN molecules were observed in the LIBS spectra of turmeric samples. Spectral signatures of toxic elements such as lead and chromium are also observed in the LIBS spectra of all samples except S6. Adulteration of metanil yellow, a toxic azo dye, is used to increase the appearance of curcumin when the actual curcumin content is low. The presence of spectral lines of lead and chromium in the LIBS spectra of S1 to S5 suggested that it may be adulterated with lead chromate which is used for coloring turmeric. Further, the presence of sulfur in EDX analysis of sample S5 indicates that it may also have been adulterated with metanil (C₁₈H₁₄N₃NaO₃S). The concentration of samples’ constituents was evaluated using CF-LIBS, and EDX was used to verify the results obtained by CF-LIBS. The principal component analysis applied to the LIBS data of the turmeric samples has been used for instant discrimination between the sample based on their constituents. We also analyzed antioxidant activity and total phenolic and flavonoid content of different turmeric samples and found a negative Pearson correlation with heavy metals. The presence of curcumin in turmeric is confirmed using LIBS and UV–Vis, which have medicinal properties. Full article

We report a quantitative analysis of various plant-biochar samples (S1, S2 and S3) by utilizing a laser-induced breakdown spectroscopy (LIBS) technique. For LIBS analysis, laser-induced microplasma was generated on the target surface by using a focused beam through a high-power Nd: YAG laser and optical emission spectra were recorded using a charged coupled device (CCD) array spectrometer, with wavelength ranges from 200 nm to 720 nm. The spectroscopical analysis showed the existence of various ingredients, including H, Li, Ca, Na, Al, Zn, Mg, Sr, Si, and Fe, along with a CN molecular emission band due to B²Σ⁺ − X²Σ⁺ electronic transition. By assuming conditions of the plasma is optically thin and in LTE, calibration-free laser-induced breakdown spectroscopy (CF-LIBS) was utilized for the compositional analysis of the ingredients present in the three plant-biochar samples. To lower the uncertainties, we used an average composition (%) of the three plant-biochar samples. The quantitative study of the plant-biochar samples was also achieved using the energy dispersive X-ray (EDX) technique, showing good agreement with the CF-LIBS technique. In addition, statistical analysis, such as principal component analysis (PCA), was performed for the clustering and classification of the three plant-biochar samples. The first three PCs explained an overall ~91% of the variation in LIBS spectral data, including PC1 (58.71%), PC2 (20.9%), and PC3 (11.4%). These findings suggest that LIBS is a robust tool for rapid measurement of heavy as well as light elements, such as H, Li, and nutritional metals in plant-biochar samples. Full article

In this work, we report the results of the compositional analysis of an aluminum gallium arsenide (AlGaAs) sample using the calibration-free laser-induced breakdown spectroscopy (CF-LIBS) technique. The AlGaAs sample was doped with three various concentrations of gallium (Ga), arsenic (As), and aluminum (Al), as reported by the manufacturer, and the CF-LIBS technique was employed to identify the doping concentration. A pulsed Q-switched Nd: YAG laser capable of delivering 200 and 400 mJ energy at 532 and 1064 nm, respectively, was focused on the target sample for ablation, and the resulting emission spectra were captured using a LIBS 2000+ spectrometer covering the spectral range from 200 to 720 nm. The emission spectra of the AlGaAs sample yielded spectral lines of Ga, As, and Al. These lines were further used to calculate the plasma parameters, including electron temperature and electron number density. The Boltzmann plot method was used to calculate the electron temperature, and the average electron temperature was found to be 5744 ± 500 K. Furthermore, the electron number density was calculated from the Stark-broadened line profile method, and the average number density was calculated to be 6.5 × 10¹⁷ cm⁻³. It is further observed that the plasma parameters including electron temperature and electron number density have an increasing trend with laser irradiance and a decreasing trend along the plume length up to 2 mm. Finally, the elemental concentrations in terms of weight percentage using the CF-LIBS method were calculated to be Ga: 94%, Al: 4.77% and As: 1.23% for sample-1; Ga: 95.63%, Al: 1.15% and As: 3.22% for sample-2; and Ga: 97.32%, Al: 0.69% and As: 1.99% for sample-3. The certified concentrations were Ga: 95%, Al: 3% and As: 2% for sample-1; Ga: 96.05%, Al: 1% and As: 2.95% for sample-2; and Ga: 97.32%, Al: 0.69% and As: 1.99% for sample-3. The concentrations measured by CF-LIBS showed good agreement with the certified values reported by the manufacturer. These findings suggest that the CF-LIBS technique opens up an avenue for the industrial application of LIBS, where quantitative/qualitative analysis of the material is highly desirable. Full article

With many advantages over well-established methods, laser induced breakdown spectroscopy (LIBS) has emerged as a useful analytical technique for the compositional analysis of multi-elemental geological materials. In this study, LIBS was employed for qualitative and quantitative analysis of a rare mineral, astrophyllite, bearing precious elements of industrial and technological interest. The experiment was carried out using second harmonic generation of Nd:YAG laser of pulse width 5 ns and repetition rate of 10 Hz. Microplasma was produced by focusing laser beam on an astrophyllite target, and optical emissions from the generated plasma were recorded in the spectral range of 200–720 nm with the help of a LIBS2000+ detection system. On analyzing the optical spectra, existence of 15 elements in astrophyllite target were revealed. These elements include: Ti, W, Ag, Al, Ba, Ca, Cr, Cu, Fe, Li, Mg, Na, Ni, Si and H. For quantification, calibration-free method was used. Only ten elements, namely Ti, W, Fe, Cr, Cu, Ca, Mg, Ni, Si and Al, were quantified with relative weight concentrations of 55.39%, 18.79%, 18.30%, 4.05%, 2.66, 0.43%, 0.18%, 0.12%, 0.06% and 0.02%, respectively. To benchmark these results, XRF analysis was performed, which confirmed the presence of all the elements detected in the optical spectrum of the sample, except for Na, Li, and H. The concentrations of these ten elements as measured by XRF were in reasonable agreement, especially for the major elements. The presence of a significant amount of Ti and W in an astrophyllite sample, found in Pakistan, highlights the economic value of this mineral. This study may be of further interest in commissioning LIBS technology for exploration of minerals in the region. Full article

We present results of calibration-free laser-induced breakdown spectroscopy (CF-LIBS) and energy-dispersive X-ray (EDX) analysis of natural colorless topaz crystal of local Pakistani origin. Topaz plasma was produced in the ambient air using a nanosecond laser pulse of width 5 ns and wavelength 532 nm. For the purpose of detection of maximum possible constituent elements within the Topaz sample, the laser fluences were varied, ranging 19.6–37.6 J·cm⁻² and optical emission from the plasma was recorded within the spectral range of 250–870 nm. The spectrum obtained has shown the presence of seven elements viz. Al, Si, F, O, H, Na and N. Results shows that the fluorine was detected at laser fluence higher than 35 J·cm⁻² and plasma temperature of >1 eV. Al and Si were found as the major compositional elements in topaz crystals. The ratios of concentrations of Al and Si were found as 1.55 and 1.59 estimated by CF-LIBS and EDX, respectively. Furthermore, no impurity was found in the investigated colorless topaz samples. Full article

Measurement of the elemental composition of shells is increasingly emerging as an avenue for obtaining high-resolution insights into paleoclimate and past seasonality. Several studies have shown significant correlations between Mg/Ca ratios measured on shell carbonate and the sea surface temperature (SST) within which this carbonate was precipitated. However, other investigations have reported large variability in this relationship between species. Therefore, further studies, including taxa previously not considered are still required in order to validate these new species as suitable climate proxies. Here, we measured Mg/Ca ratios for limpet Patella depressa Pennant, 1777 samples live-collected in northern Spain for the first time. The elemental ratio was measured using laser-induced breakdown spectroscopy (LIBS), a technique that significantly decreases the time required for sample preparation and increases the number of shells that can be analyzed. In this study, calibration-free LIBS (CF-LIBS) methods were applied to estimate molar concentrations of chemical elements on biogenic calcium carbonate. The Mg/Ca ratio evolution along the shell growth axis was compared with stable oxygen isotope (δ¹⁸O) profiles obtained from these same limpets and the SST at the place where the mollusk grew to determine if the sequences obtained correctly reflected environmental conditions during the life-span of the mollusk. The results showed a significant correlation between Mg/Ca ratio series and both δ¹⁸O profiles and SST, highlighting the paleoenvironmental and archaeological potential of LIBS analyses on this mollusk species that is frequently found in archaeological contexts in the western Europe. Full article

We coated graphitic nanocarbons by thermal chemical vapor deposition (CVD) on silicon flakes recycled from the waste of silicon wafer manufacturing processes as an active material for the anode of lithium ion battery (LIB). Ferrocene contains both iron catalyst and carbon, while camphor serves as an additional carbon source. Water vapor promotes catalytic growth of nanocarbons, including carbon nanotubes (CNTs), carbon fibers (CFs), and carbon films made of graphitic carbon nanoparticles, at temperatures ranging from 650 to 850 °C. The container of silicon flakes rotates for uniform coatings on silicon flakes of about 100 nm thick and 800–1000 nm in lateral dimensions. Due to short CVD time, besides CNTs and CFs, surfaces of silicon flakes deposit with high-density graphitic nanoparticles, especially at a low temperature of 650 °C. Nanocarbon coatings were characterized by SEM, EDX, ESCA, and Raman spectroscopy. Half-cells were characterized by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and retention of capacity in discharge/charge cycling. Silicon-flake-based anode with nanocarbon coatings at both 650 and 850 °C exhibited capacity retention of 2000 mAh/g after 100 cycles at 0.1 C, without needing any conductivity enhancement material such as Super P. Full article