BUKU PROSIDING

analysis under a nitrogen atmosphere. This study aimed to determine the effects of quaternization reaction on the thermal properties including thermal stability at 5% weight loss ( ), maximum decompisition temperature ( ), and total weight lost percentage (wt.%) derived from TGA analysis. Additionally, phase transition behaviour and fusion entropy (>Sf) were examined for lauric acid, tris-3-aminopropylamine (TPA), and the resultans FA and TAS.The TGA thermograms and first derivative thermogravimetric (DTG) curves for thermal decomposition of FA and RAS are ilustrated in )LJXUH Weight lost percentage (wt.%) and thermal behaviour values are summarized in 7DEOHGenerally, all samplesexhibited approximatelt 1 wt.% weight loss within the 20-100 ? range, attributed to moisture evaporation and residual solvent loss. Thermal stability of amide reaction products was observed in FA, showing a 5% weight reduction at a of 366 ?, with the DTG curve reaching a at 366 ?. The TGA curve od FA reveal a single decomposition phase ( ), corresponding to the breakdown of FA structure via three degradation mechanisms for fatty amide bonds. The primary mechanism involves the decomposition of FA to form a primary amine and carboxylic acis, followed by secondary mechanism involving the decomposition of primary amine and carboxylic groups [15].)LJXUH TGA thermograms and DTG curves of FA andTAS As shown in )LJXUH  the quaternization reaction toproduce TAS exhibits a lower weight reduction percentage compared to FA, with the of 250 ? for TAS. The TGA and DTG thermograms indicate that TAS samples undergo three decomposition phases, designated mp, ,and rg. Similar TGA analysis findings for conventional TAS have been reported by H.Liu et al. [16] and Kleijwegt et al.[17], outlining three TAS decomposition phases: i) thermal decompisition of intercalated TAS cations, ii) amide chain degradation, and iii) hydroxyl group removal. The first decomposition ( ), occurs between 100 ? and 350 ?, reaching peak decomposition temperatures of 250 ? for TAS. This phase likely corresponds to high temperature decomposition of TAS cations. The Hoffmans elimination is considered the primary reaction pathway, involving nucleophilic attack by anions on the @-hydrogen rather than on the nitrogen atom. This reaction detaches the long chain from nitrogen, yielding alkenes, tertiary amines, and protonated anions. Another proposed mechanism is nucleophilic elimination on the carbon of the long chain substituent , leading to the formation of alkane structures containing TAS anions alongside tertiary amines. This reaction pathway generally exerts a less significant effect on decomposition under most conditions.7DEOH Weight loss percentage (wt. %) of FA andTAS6DPSOH !%(*C):HLJKWORVVZW7RWDOZHLJKWORVVSHUFHQWDJHZW5HVLGXHDIWHU ƕ&\"# ,350-400 *C)$ 366 - 98 - 98 2\"# ,100-350*C\"$,350-380*C\"%,380-400*C7$6 250 69 22 5 96 4The second decomposition stage ( ) for TAS exhibits approximately 22% weight loss with a at 369 ?. This phase is associated with the breakdown of amide groups, resulting in the formation of carboxylic acids and water, consistent with the previous findings on amide thermal degradation [18]. The third decomposition stage ( ) begins in the 380-400 ? range, corresponding to the decomposition of carboxylic acids into carbon dioxide and water [19]. Similar findings were reported by H. Liu et al. where the third stage of quaternary ammoniumsalt decomposition occured within the 450-700 ? range.During the pong , TAS shows approximately 5% loss at a of 409 ? attributed to molecular weight variations [20].In general, FA synthesized through carboxylic acid features long, hydrophobic alkyl chains. These extended alkyl chains enhance thermal stability due to increased molecular weight and stronger van der Waals interactions between adjacent chain [15], resulting in a higher decomposition temperature decomposition temperature of FA. Conversely, TAS which includes a positively charged nitrogen atom bonded to four alkyl groups, undergoes multiple thermal decomposition stages. .219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7292

pahse transition temperature (Findings from this study indicate that TAS decomposes at lower temperatures than FA, possibly due to TAS purity not yeat reaching optimal levels, as previously discussed in th mass spectroscopy characterization. Additionally, the presence of ionic bonds and the more complex TAS structure may further constribute to reduce thermal stability [21].The thermal behaviour of synthesized FA and TAS was further analyzed using DSC, as shown in )LJXUH with the thermal property values summarized in 7DEOH. Based on DSC thermogram, the melting temperature( ) of FA purified via LLE is 33 °C, with a solid-solid) at 113°C.The enthalphy value for FA was analyzed as 64.01 kJmol-1 and entropy was found to be 165.77 JK-1mol-1. This study found no significance difference in and values for FA with or without LLE purification, previously recorded at 39 °C and 113 °C, respectively [4]. The observed entropy is within the range of other FA examined in previous studies, around 172-196 JK-1mol-1[22].Conversely, the DSC thermogram of TAS synthesized from FA with LLE shows stable values at at 71°C during first heating cycle and 87 °C during the second. The g value remains unchanged across both cycles at 106 °C, with enthalphy and entropy values of 47.28 kJmol-1 and 124.43 JK-1mol-1, respectively ()LJXUH). The values for TAS observed in this study arenotably higher than those reported for non purified TAS, previously recorded at 47 °C (first heating cycle) and 30 °C (second heating cycle) [4]. As discussed in the previous spectroscopy subtopic, LLE purification effectively removed unreacted residual reactants, yielding a purer product. This increased putrity enhances crystallinity and alters the molecular structure od TAS, leading to higher transition temperature [5].The thermal behavior of FA and TAS synthesized was further analyzed using DSC techniques. The sample heat readings were erased during the first heating. The DSC traces corresponding to the second cooling and heating cycles are shown in )LJXUH Based on the nginformationobtained from TGA analysis, the maximum DSC heating temperature was set at 366 ? for FA samples and 250 ? for TAS samples. The sample heat readings were erased during the first heating. The DSC traces corresponding to the second cooling and heating cycles are shown in )LJXUH. 7DEOH  presents the results measured by DSC,including the values of each measured property in the lasttwo cycles of a three-sequence run. This list only includessolid compounds that exhibit phase change transitionsunder the specified experimental conditions. In this data,phase change temperatures are determined by peaktemperature, whereas phase change enthalpy is shown as anormalized parameter calculated by integrating the areaunder each peak. The melting temperature ( ) of the analyzed materials ranges from 118 °C to 119 °C, while the solid-solid transition temperature ( ) ranges from 79 °C to 85 °C. According to the thermogram, the value for FA with LLE purification is 33.1°C, and the value is 112.8 °C. The enthalpy of the analyzed fatty amide is 64.01 kJ/mol, while the entropy value is 165.77 J/K.mol. The study found no significant difference in Ts-sand Tm values between LLE-purified FA and non-purified FA previously conducted by (F. N. Jumaah et al. 2023). These enthalpy and entropy values are within the range of several FAs studied in previous research, around 172-196 kJ/kg, although they are lower than otherdiamides described (190 and 210 J/K.mol). Overall, FAcompounds show small differences in l), enthalpy, and entropy changes between the first and second cycles. Conversely, the thermogram of TAS synthesized from fatty amide with LLE purification shows a stable value of 71°C (first heating cycle) and 87°C (second heating cycle). The (value obtained for TAS was found to be twice as high compared to previous reports on TAS without purification. The for TAS with LLE purification occurs at 106°C with recorded enthalpy and entropy values of 74.25 kJ/mol and 196.34 J/K.mol, respectively. Additionally, longer alkyl chains can increase the overall molecular size and shape, affecting molecular interactions and the stability of TAS. This can result in a less ordered and more fluid-like structure, contributing to lower and values. Spectroscopic analysis in the previous subsection demonstrated that LLE purification successfully removed residues and unreacted materials, leading to a purer product [11]. This increase in purity can result in better crystallinity and molecular solid-state efficiency of TAS, which in turn can lead to higher transition temperatures. Furthermore, residues and unreacted materials in impure fatty amides can disrupt molecular arrangement and interactions within TAS crystals, potentially lowering transition temperatures [4, 23]. 6\\QWKHVLV RI 3HURYVNLWH 0DWHULDOV DQG 'HYLFH(IILFLHQF\\5DPDQVSHFWURVFRS\\DQDO\\VLV)LJXUH  presents the Raman spectra of perovskite filmswith the composition TASxMAI1-xPbI3 deposited on glass substrates at varying molar fractions (with x=0.01, 0.03 and 0.05) within the wavenumber range of 50 cm-1 to 300 cm-1. Referring to the theoretical and experimentalcomparisons on MAPbI3 and PbI2 conducted by Pistor etal. [24] and Kong et al. [25] , the characteristicwavenumber for MAPbI3 were identified at 103 cm-1, 122cm-1, 138 cm-1, 204 cm-1 and 246 cm-1. In contrast, PbI2exhibit peaks at 96 cm-1, 117 cm-1, 166 cm-1 and 220 cm-1.293.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7

In this study, the peaks corresponding to MAPbI3 wereobserved at 52 cm-1, 71 cm-1, 108 cm-1, 122 cm-1 and 248 cm-1 which is align well with the previous reported data[24, 25].)LJXUH Raman spectra for TASxMAI1-xPbI3 perovskitefilms with sprespectively.Future observations focused on the impact of TAS incorporation into the MAPbI3 structure with varying molar fractions of TASxMAI1-xPbI3. The addition of TAS from x=0.01 to x=0.05 revealed peaks within the wavenumber range constant with MAPbI3. Notably, significant changes in peaks intensity were observed in the range of 108 cm-1and 122 cm-1, representing the decomposition and stretching vibrations of PbI2, particularly with TAS0.01MAI0.99PbI3 [26]. The incorporation of 1% TAS was also found to enhance the intensity and sharpeness of the peak , corresponding to the MAPbI3 twisting mode and vibrational modes (including symmetric and asymmetric stretching, as well as bending) of organic cations [27]. At higher TAS molar fractions, changes in the intensity and peak shifts were also observed at the wavenumber 52 cm-1,indicating structural modifications induced by TAS incorporation.The intensity variation and peak shifts in Raman spectra highlight changes in the inorganic components of the crystal structure, particularly the bending mode I-Pb-Iand the stretching mode Pb-I [28]. The addition of 3% and 5% TAS reveals the presence of decomposition-related associated with the Pb-I stretching modes at wavenumbers ranging from 108 cm-1 to 122 cm-1, as well as at 248 cm-1[29]. However, the intensities of these peaks diminish with increasing TAS molar fraction.It is well-established that MAPbI3 perovskite structures decompose readily into PbI2 under conditions of moisture exposure, irradiation, and thermal stress exceeding 100oC [30, 31]. Consequently, PbI2 is often detected in degraded MAPbI3 thin films, typically as a result of excessive heating and radiation exposure [32]. In this study, decomposition of the perovskite thin films into PbI2 is not observed, as the characteristic peaks corresponding to PbI2 degradation within wavenumber 94-97 cm-1 and 219-220 cm-1 are absent in the Raman spectra [24].&U\\VWDOOLQLW\\SURSHUWLHVThrough this characterization, the thin films of perovskite TASxMAI1-xPbI3 were successfully deposited on glass substrate surfaces. )LJXUH  shows the XRD patterns ofTASxMAI1-xPbI3 films with x = 0, 0.01, 0.03, and 0.05. The observed XRD peaks at 14.7°, 19.5°, 23.6°, 24.6°, 28.4°, 31.7° and 34.9° correspond to the crystallographic planes (110), (112), (211), (202), (220), (222) and (314) of the MAPbI3 perovskite crystal structure. The results confirm the presence of the crystalline perovskite phase with a tetragonal lattice structure, consistent with previous reports and matched with the PDF#01-085-508 reference pattern. Notably, no peaks corresponding to the decomposition phase of PbI2 were detected, further validating the high purity and structural integrity of the MAPbI3 films [12]. ,QWHQVLW\\DX0$3E,7$60$ffiffi3E,7$60$ffi3E,7$60$ffi3E,(110) (220) (222) (011) (112) (211) (202) (204) (004)7KHWD      3')flfl)LJXUH The XRD patterns for TASxMAI1-xPbI3 derivedfrom perovskite precursor solutions with p prrespectively. The films were deposited on glass substrates.)LJXUHflD and flE illustrate the enlarged XRDpeaks in the range of 13°-29°. A shift towards higher 2- values is observed in )LJXUH flD with addition of TASmolar fractions into the MAPbI3 thin films. This shift indicated compressive strain in the TASxMAI1-xPbI3perovskite films compared to the control MAPbI3 film. When 1% TAS molar fractions is added, the intensity of the (110) peak increases, accompanied by sharper resolution relative to the MAPbI3 peak. This change in peak intensity suggests a structural transformation form a 3D perovskite layer to a 2D configuration [28]. .219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7294

Furthermore, the addition of TAS molar fractions to the MAPbI3 structure significantly impacts the dissappearance of the (004) peak in the MAPbI3 peak film while enhancing the (220) peak intensity at 28.4° in the TASxMAI1-xPbI3structure. This effect is attributed to lattice compressivestrain at the (220) peak in the TASxMAI1-xPbI3 thin films, as shown in )LJXUHflE.The crystallite size was observed to increase from 25.31 nm (MAPbI3) to 33.78 nm with the addition of 1% TAS (7DEOH ). A further increase in crystallite size wasnoted with 3% TAS, reaching 33.92 nm. However, at 5% TAS, the crystallite size stabilized and remained unchanges at 33.92 nm. The lattice strain ( ) and crystallinity percentage for MAPbI3 ( =0.32, 93.62%) showed improvements with the addition of TAS molar fractions, with respective values for TAS0.01MAI0.99PbI3 ( =0.53, 97.84%), TAS0.03MAI0.97PbI3 ( =0.44, 92.89%) and TAS0.05MAI0.95PbI3 ( =0.46, 84.13%) (7DEOH ).Differences in energy absorption by the percursors promoted nucleation and crystallization, leadind to variations in strain and crystallinity percentage [31]. The XRD diffractions analysis revealed that TAS0.01MAI0.99PbI3 film exhibited the highest lattice strain and crystallinity percentage.7DEOH The lattice structure parameters forTASxMAI1-xPbI36DPSOHĂсď;Ϳ Đ;Ϳ /DWWLFH*UDLQVL]H&''LVORFDWLRQGHQVLW\\(&'($)#*(%)/DWWLFHVWUDLQ +)&U\\VWDOOLQLW\\MAPbI3 8.85 12.69 Tetragonal 25.31 0.69 0.32 93.62TAS0.01MAI0.99PbI3 8.80 12.65 Tetragonal 33.78 0.68 0.53 97.84TAS0.03MAI0.97PbI3 8.80 12.65 Tetragonal 33.92 0.66 0.44 92.89TAS0.05MAI0.95PbI3 8.81 12.62 Tetragonal 33.92 0.75 0.46 84.13The discolation density (<) was also calculated to evaluate the number of discolations within the crystalline material. Several recent studies have examined the effects of strain to minimize discolation density. The introduction of TAS in crystalline lattice altered its structural properties, including strain that influenced discolation behaviour [33]. Although TAS increased strain energy, it improved crystallinity and reduce discolations at lower molar fractions. Reducing discolation density in semiconductor substrates is crucial for fabricating high-quality PSC devices. Additionally, the FWHM values for (110) and (220) peaks showed increased in intensity and sharperresolution, indicating better crystallinity as TAS molarfraction increased from 1% to 5%, as illustrated in )LJXUHfl. The presence of TAS significantly enhance the stabilityof MAPbI3 perovskite films by reducing theirdecomposition rate to PbI2 under enviromental conditions.This alligns with previous reports indicating that Pb atoms influence surface imperfections in films, leading to a decline perovskite device performance [34ñ36].0RUSKRORJ\\SURSHUWLHV)LJXUHffi depicts SEM images of the device structuresof MAPbI3 and TAS0.01MAI0.99PbI3 device structures. The cross-sectional image of reveals small grain sized with a smooth surface and uniform distribution of lead and iodide, consistent with previous findings by Ren et a. [37]. The inclusion of TAS0.01MAI0.99PbI3 resulted in a compaction of the perovskite layer , reducing its thickness from 390 nm to 381 nm. Based on the XRD analysis presented earlier, TAS was found to increase the crystallize size from 25.31 nm in MAPbI3 to 33.78 nm in TAS0.01MAI0.99PbI3accompanied by a significant improvement in crystallinity to 98%. This structural compaction and crystallite growth in the perovskite layer are likely due to TAS facilitating better crystal growth, reducing nucleation, and enhancing surface coverage, leading to higher crystallinity. These findings are further supported by studies conducted by Banerjee et al. [38] and Banik et al. [34], which investigated the effects of using commercial TAS as a precursor in perovskite layers. The addition of TAS improves crystallinity and increases crystallite size while reducing defects in the light-absorbing layer and minimizing recombination at the MAPbI3 surface [39]. This structural enhancement is crucial for optimizing the performance of PSC devices.)LJXUHffiThe cross-sectional morphology of theTASxMAI1-xPbI3 device through SEM characterization analysis.2SWLFDOSURSHUWLHV)LJXUHD shows the images of annealed perovskitefilms prepared with TASxMAI1-xPbI3 at varying molar fractions (x=0, 0.01, 0.03 and 0.05). All films appear black and refelctive after heating 70oC for 15 minutes. Increasing the molar fraction does not alter the colour of the perovskite films compared to the control film. However, distinct colour changes are observed after the filmd are left for seven days, as shown in )LJXUH E. The filmsTAS0.03MAI0.97PbI3 and TAS0.05MAI0.95PbI3 display a transition from black to brownish tones, with further fadinf .219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7295

over time. In contrast, the colour of the MAPbI3 andTAS0.01MAI0.99PbI3 films remain unchanged. This phenomenon is attributed to a reduction in the dimentionality of the perovskite crystal structure, transitioning to layed perovskite crystal grains.This observation aligns with the absorption spectra and XRD findings, which will be discussed in subsequent sections. Notab;y, these physical colour changes are unrelated to film thickness, which was measured using a profilometer and found to be consistent 300-350 nm. )LJXUH  presents the Tauc plots for the perovskitefilms derived from UV-Vis spectra. The band gap (Eg) of the material can be determined using these absorption edges and Taucís formula, rmined= A(h! \" Eg) [30].Here, the absorption coefficient is denoted by #, where A is a constant, and h$ represents the energy of the incoming photon. Since the perovskite is a semiconductor with a direct bandgap material, the Tauc plot can be constructed for n equal to 0.5. The optical bandgap value for the control film was determined to be 1.590 eV, consistent with findings from previous studies [40]. From the Taucanalysis, the optical bandgap values for perovskite films showed no significant changes with increasing TAS molar fractions (x=0, 0.01, 0.03 and 0.05), yielding values of 1.599 eV, 1.592 eV and 1.604 eV, respectively (7DEOH).This observation, that the bandgap values remain unaffected by TAS incorporation , is crucial as it indicated that the use of TAS as a precursor does not compromise the fundamental properties of perovskites required for PSC performance. This ensure that, alongside the potential for enhanced stability and the environmentally friendly nature of TAS compared to conventional precursors, the optical performance of the material in solar cell applications is maintained, This make TAS as a promising material for sustainable PSC development [28, 41].)LJXUH The UV-Vis absorption spectra and Tauc plotfor TASxMAI1-xPbI3 perovskite films prepared on glass substrates with pe p parespectively.3KRWRYROWDLFSURSHUWLHVThe performance of photovoltaic devices was evaluated through current density-voltage (J-V)measurements for PSC configured as of FTO/c-TiO2/mTiO2/TASxMAI1-xPbI3/Spiro-OMeTAD/Ag, as shown in )LJXUH . Device parameters, including open-circuitvoltage (VOC), short-circuit current density (JSC), maximum voltage (Vmax), fill factor (FF), and power conversion efficiency (PCE), were determined and summarized in 7DEOH . This study primarily focused on characterizingthe initial photovoltaic properties of TAS-based PSC, without optimizing the device fabrication for maximum efficiency. The control PSC device based on MAPbI3exhibited VOC, JSC, FF, and PCE values of 0.75V, JSC of 10.3 mAcm-2, FF of 57.25% and PCE of 4.40%. Incorporating a 3% molar fraction of TASas a precursor improved the FF to 60.10%, while JSC stabilized at a 10.10 mAcm-2. These enhancements in FF and JSC can be attributed to enhanced charge transfer and improved electron mobility facilitated by the TAS structure [34, 38]. Device fabricated with showed TAS0.01MAI0.99PbI3significant improvement in VOC and Vmax, reaching 0.56V. This enhancement aligns with the XRD findings, indicating increased crystallinity of the perovskite films due to TAS incorporation. The higher crystallinity likely arises from reduced defects within the perovskite later, enabling better change transport and minimizing charge recombination. Consequently, higher VOC values were achieved, as reduced recombination losses allow more change carriers to reach the electrodes [42]. The optimal PCE for TASincorporated devices was recorded at 3.90% for TAS0.01MAI0.99PbI3, followed by 3.70% for TAS0.03MAI0.97PbI3 and TAS0.01MAI0.99PbI3. While the control PSC (4.40%) slightly outperformed TAS-based devices, the preliminary results underscore the potential of TAS as a precursor in enhancing crystalline and improving charge transport properties in perovskite layers. These findings suggest that TAS incorporation offers a promising pathway for tailoring the structural and electronic properties of PSC, with further optimizing expected to enhance overall efficiency and stability. )LJXUH curves for moderately performing devices based on perovskite and mixed TASxMAI1-xPbI3 with x = 0.01, 0.03, 0.05 respectively.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7296

7DEOH Photovoltaic parameters of FTO/c-TiO2/mTiO2/ TASxMAI1-xPbI3/Spiro-OMeTAD/Ag with different mol fraction of TAS precursor 6DPSOH !\"9 #$\" P$FP %&' 9 ((  )\"* +,)-./ 0.75 10.30 0.55 57.25 4.400,$1.12+,.1.33)-./ 0.81 8.80 0.56 45.97 3.900,$1.1/+,.1.34)-./ 0.61 6.00 0.54 60.10 3.700,$1.15+,.1.35)-./ 0.76 10.10 0.49 48.90 3.70 &21&/86,21This study highlights the significant potential of highpurity bio-based TAS as sustainable and efficient materials for PSC. The research successfully demonstrates the synthesis and optimization of bio-based FA and TAS through an enhanced procedural method incorporating LLE, resulting in high-purity products. The optimized synthesis parameters yielded a 100% abundance of trisubstitution bio-based FA and enhanced TAS purity up to 60%, as confirmed by mass spectroscopy. DSC analyses revealed that FA with LLE purification exhibited a ysof 113°C and a solid-solid transition temperature of 33°C, while TAS synthesized from FA showed a of 106°C and a syof 77°C. This significant increase in , compared to previous reports on TAS without LLE purification, indicates that the LLE process effectively eliminated residues and unreacted materials, enhancing crystallinity, and resulting in a product with the characteristics of an ionic liquid crystal. Although TAS exhibited lower thermal stability ( = 250°C) compared to FA ( = 366°C), its application as a precursor in C), apmol fractions demonstrated a notable reduction in the energy bandgap (Eg = 1.592-1.604 eV) compared to the MAPbI3 control structure (Eg = 1.590 eV). XRD analysis confirmed that TAS incorporation significantly enhances perovskite crystallinity, increasing it from 94% to 98% for TASxMAI1-xPbI3. This improvement is attributed to reduced crystal nucleation, the formation of homogeneous large crystals, and fewer pinholes. The PCE of the PSC configuration FTO/TiO2/ TASxMAI1-xPbI3/SpiroOMeTAD/Ag reached an optimum of 3.90% for the TAS0.01MAI0.99PbI3 mol fraction, with , and values of 8.80 mAcm-2, 0.81 V, and 45.97, respectively. Overall, this research establishes high-purity bio-based FA as a viable and sustainable precursor for TAS production, demonstrating its immense potential for developing highly efficient and environmentally friendly PSC. The findings underscore the importance of optimizing synthesis parameters and purification processes to enhance the performance and stability of bio-based materials in renewable energy applications.$&.12:/('*(0(17This research was funded by the Ministry of Higher Education (MOHE) through Fundamental Research Grant Scheme (FRGS) under the grant number FRGS/1/2022/TK08/UKM/02/15. The authors thank the UKM, and Solar Energy Research Institute (SERI) for allowing this research to be carried out. Appreciation to PhD Scholarship, Hadiah Latihan Persekutuan (HLP) support to Ts. Dr. Nur Maizura Mustafa by Public Service Department of Malaysia (JPA).5()(5(1&(6[1] Hoefler SF, Trimmel G, Rath T. Progress on lead-freemetal halide perovskites for photovoltaic applications: areview. Monatshefte fur Chemie 2017; 148: 795ñ826.[2] Pandey R, Bhattarai S, Sharma K, et al. HalideComposition Engineered a Non-Toxic Perovskite-SiliconTandem Solar Cell with 30.7% Conversion Efficiency.ACS Appl Electron Mater 2023; 5: 5303ñ5315.[3] Werlinger F, Segura C, MartÌnez J, et al. CurrentProgress of Efficient Active Layers for Organic,Chalcogenide and Perovskite-Based Solar Cells: APerspective. Energies (Basel); 16. Epub ahead of print2023. DOI: 10.3390/en16165868.[4] Jumaah FN, Mustafa NM, Mobarak NN, et al. Biobased quaternary ammonium salt as an electrolyte for dyesensitised solar cells. Electrochim Acta 2023; 472: 143383.[5] Okeke UC, Snyder CR, Frukhtbeyn SA. Synthesis,purification and characterization of polymerizablemultifunctional quaternary ammonium compounds.Molecules; 24. Epub ahead of print 13 April 2019. DOI:10.3390/molecules24081464.[6] Rao S, B.T N, Preman NK, et al. Synthesis,characterization, and evaluation of quaternary ammoniumbased polymerizable antimicrobial monomers forprosthodontic applications. Heliyon 2022; 8: e10374.[7] Kim H, Lee SU, Lee DY, et al. Optimal InterfacialEngineering with Different Length of AlkylammoniumHalide for Efficient and Stable Perovskite Solar Cells. AdvEnergy Mater; 9. Epub ahead of print 1 December 2019.DOI: 10.1002/aenm.201902740.[8] Chen ZZ, Gang HZ, Liu JF, et al. A thermal-stable andsalt-tolerant biobased zwitterionic surfactant with ultralowinterfacial tension between crude oil and formation brine. JPet Sci Eng 2019; 181: 106181.[9] Mustafa NM, Jumaah FN, Ludin NA, et al.Tetraalkylammonium salts (TAS) in solar energyapplications ñ A review on in vitro and in vivo toxicity.Heliyon 2024; 10: e27381.[10] M.S. Suíait, A.Ahmad, K. H. Badri, et al. Methodof Producing Palm-based Quarternary Ammonium Salt,.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7297

Intellectual Property Corporation of Malaysia, Kuala Lumpur, Malaysia, 2019, Patent Filed No. PI2019007890, 2019.[11] Mustafa NM, Jumaah FN, Yoshizawa-fujita M, etal. Impacts of synthesis variables on spectroscopicsevaluation of biobased fatty amide as alkylammoniumsaltís precursor for perovskite. Constr Build Mater 2024;428: 136283.[12] Miura YF, Akagi Y, Hishida D, et al. TwoDimensional Layered Organic-Inorganic Hybrid PerovskiteThin-Film Fabrication by Langmuir-Blodgett andIntercalation Techniques. ACS Omega 2022; 7: 47812ñ47820.[13] Hamaguchi R, Yoshizawa-Fujita M, Miyasaka T,et al. Formamidine and cesium-based quasi-twodimensional perovskites as photovoltaic absorbers.Chemical Communications 2017; 53: 4366ñ4369.[14] Lee MK, Wang SJ, Jurysta M, et al. Comparisonof Electrospray Ionization and Fast Atom BombardmentMass Spectrometry for the Analysis of Saponins fromAlfalfa, Clover, and Mungbeans. Journal of the ChineseChemical Society 1996; 1: 315ñ320.[15] Zheng Y, Martinez CJ, Youngblood JP. Synthesisand characterization of long-chain (C20 ~ C48) fatty acidamides (FAAms) from soybean oil and alkyl amines forphase change material applications. J Appl Polym Sci2023; 140: 1ñ12.[16] Liu H, Guo C, Cui Y, et al. Experimental andmodeling investigation of organic modifiedmontmorillonite with octyl quaternary ammonium salt. SciRep 2022; 12: 1ñ10.[17] Kleijwegt RJT, Winkenwerder W, Baan W, et al.Degradation kinetics and solvent effects of various longchain quaternary ammonium salts. Int J Chem Kinet 2022;54: 16ñ27.[18] M‰nnle F, Rosquist Tofteberg T, Skaugen M, etal. Polymer nanocomposite coatings based on polyhedraloligosilsesquioxanes: Route for industrial manufacturingand barrier properties. Journal of Nanoparticle Research2011; 13: 4691ñ4701.[19] Fan M, Ma L, Zhang C, et al. Biobased GreenLubricants: Physicochemical, Tribological andToxicological Properties of Fatty Acid Ionic Liquids.Tribology Transactions 2018; 61: 195ñ206.[20] Bavisotto R, Rana R, Hopper N, et al. Influence ofthe terminal group on the thermal decomposition reactionsof carboxylic acids on copper: Nature of the carbonaceousfilm. Physical Chemistry Chemical Physics 2021; 23:17663ñ17671.[21] Iniesta-LÛpez E, Hern·ndez-Fern·ndez A,MartÌnez-LÛpez £, et al. Characterization of QuaternaryAmmonium-Based Ionogel Membranes for Application inProton Exchange Membrane Fuel Cells. Gels; 10. Epubahead of print 2024. DOI: 10.3390/gels10050308.[22] Papadopoulos L, Kluge M, Bikiaris DN, et al.Straightforward synthetic protocol to bio-based unsaturatedpoly(ester amide)s from itaconic acid with thixotropic behavior. Polymers (Basel) 2020; 12: 1ñ16.[23] Jumaah FN, Mobarak NN, Hassan NH, et al.Review of non-crystalline and crystalline quaternaryammonium ions: Classification, structural and thermalinsight into tetraalkylammonium ions. J Mol Liq 2023;376: 121378.[24] Pistor P, Ruiz A, Cabot A, et al. Advanced RamanSpectroscopy of Methylammonium Lead Iodide:Development of a Non-destructive CharacterisationMethodology. Sci Rep 2016; 6: 1ñ8.[25] Kong W, Rahimi-Iman A, Bi G, et al. OxygenIntercalation Induced by Photocatalysis on the Surface ofHybrid Lead Halide Perovskites. Journal of PhysicalChemistry C 2016; 120: 7606ñ7611.[26] StefaQska D, Ptak M, MUczka M. Synthesis,Photoluminescence and Vibrational Properties ofAziridinium Lead Halide Perovskites. Molecules; 27. Epubahead of print 2022. DOI: 10.3390/molecules27227949.[27] Ardimas, Pakornchote T, Sukmas W, et al. Phasetransformations and vibrational properties of hybridorganicñinorganic perovskite MAPbI3 bulk at highpressure. Sci Rep 2023; 13: 1ñ12.[28] Rebecca LWX, Burhanudin ZA, Abdullah M, etal. Structural changes and band gap tunability withincorporation of n-butylammonium iodide in perovskitethin film. Heliyon 2020; 6: e03364.[29] PÈrez-Osorio MA, Lin Q, Phillips RT, et al.Raman Spectrum of the Organic-Inorganic HalidePerovskite CH3NH3PbI3 from First Principles and HighResolution Low-Temperature Raman Measurements.Journal of Physical Chemistry C 2018; 122: 21703ñ21717.[30] Ming-Chen Tsai, Chu S-Y, Kao P-C. PerformanceEnhancement of Three-Dimensional MAPbI3 PerovskiteSolar Cells by Doping Perovskite Films with CsPbX3Quantum Dots. Materials 2024; 17: 1238.[31] Ullah A, Khan MI, Ihtisham-ul-haq, et al. Transpolyacetylene doped Cs2AgBiBr6: Band gap reduction forhigh-efficiency lead-free double perovskite solar cells.Results Phys 2024; 60: 107654.[32] Bartie N, Cobos-Becerra L, Mathies F, et al. Costversus environment? Combined life cycle, technoeconomic, and circularity assessment of silicon- andperovskite-based photovoltaic systems. J Ind Ecol 2023;27: 993ñ1007.[33] PeöiVka J, Kuûel R, Dronhofer A, et al. Theevolution of dislocation density during heat treatment andcreep of tempered martensite ferritic steels. Acta Mater2003; 51: 4847ñ4862.[34] Banik BK, Banerjee B, Kaur G, et al.Tetrabutylammonium Bromide (TBAB) CatalyzedSynthesis of Bioactive Heterocycles Bimal. Rev J Chem2020; 4: 221ñ251.[35] Liu S, Gonzalez M, Kong C, et al. Synthesis,antibiotic structureñactivity relationships, and cellulose.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7298

dissolution studies of new room-temperature ionic liquidsderived from lignin. Biotechnol Biofuels 2021; 14: 1ñ10.[36] Poli I, Eslava S, Cameron P. Tetrabutylammonium cations for moisture-resistant and semitransparent perovskite solar cells. J Mater Chem A Mater 2017; 5: 22325ñ22333.[37] Ren J, Zhai G, Chen Q, et al. Effect of reactiontemperature on film quality and cell performance:Comparative study of single and mixed cation/halideperovskites. Mater Sci Semicond Process; 150. Epub aheadof print 2022. DOI: 10.1016/j.mssp.2022.106952.[38] Banerjee S, Gayen RN. Tetramethylammoniumbased lead free perovskite active layer for solar cellapplication. Ceram Int 2019; 45: 17438ñ17441.[39] Wu H, Deng Z, Zhou B, et al. Improvedtransdermal permeability of ibuprofen by ionic liquidtechnology: Correlation between counterion structure andthe physicochemical and biological properties. J Mol Liq2019; 283: 399ñ409.[40] Mohamad Noh MF, Arzaee NA, Nawas MumthasIN, et al. Facile tuning of PbI2 porosity via additiveengineering for humid air processable perovskite solarcells. Electrochim Acta 2022; 402: 139530.[41] Cao DH, Stoumpos CC, Farha OK, et al. 2DHomologous Perovskites as Light-Absorbing Materials forSolar Cell Applications. J Am Chem Soc 2015; 137: 7843ñ7850.[42] Jiang Y, Dong R, Cai X, et al. Effect ofAmphiphilic Quaternary Ammonium Salt Additive onPerformance and Stability of Perovskite Solar Cells.Gaodeng Xuexiao Huaxue Xuebao/Chemical Journal ofChinese Universities; 40. Epub ahead of print 2019. DOI:10.7503/cjcu20190024..219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7299

!\"#\"$%&\"'%()*+\",,-.(/-%0123-4 5.6\"*3&*7(\"(8&231#\"2(930*0:$(+;2017;(/\"2-(9\"2+;(9#-:-*+%(/-306-2$(<20:(!-+\"##&3(!&*-(=\"%+-Mohd Zaid Md Sharif1,2, Mohd Syahrir Mohd Rozi1, Wan Adriana Zahirah Mior Ahmad Zaini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`BaJK!.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7300Abstract: Rare earth elements (REEs) are critical to modern technologies, supporting renewable energy, electric vehicles, electronics, and defense systems. Global demand is rising, yet supply remains vulnerable due to geopolitical and environmental constraints. In Malaysia, REEs extraction efforts have focused on primary sources such as monazite, xenotime, and ion-adsorption clays. However, vast volumes of metallic mine waste such as acid mine drainage (AMD) remain underutilized despite their potential as secondary REEs sources. This study investigates REEs recovery from AMD at three metallic mine sites in Peninsular Malaysia. Laboratory-scale extraction revealed that one site produced REEs concentrations comparable to low-grade primary ores. Recovery results were consistent across trials, validating the reliability of the extraction method. These findings highlight the potential to transform environmental liabilities into strategic resources. A national initiative to map and characterize REEs content in mine waste is recommended to support a circular REEs economy. Furthermore, development of this sector could directly benefit Malaysia’s Technical and Vocational Education and Training (TVET) programs by creating skilled workforce opportunities in green technology, mineral processing, and resource recovery. Harnessing these secondary sources can reduce import dependency, promote sustainable development, and position Malaysia as a competitor in regional rare earth production. Keywords: Rare earth elements, strategic mineral, acid mine drainage, recovery, secondary source

,-(),317'$/&! I.98&B_JK! (%5! ('+&%317'$/&! I8&@+BJ! $%! /-&!1'&+&%,&! 34! 3N7<&%! (%5!L(/&'K! <&%&'(/$%<! (,$5$,! &44)9&%/+!)(5&%!L$/-!5$++3)?&5!2&/()+!!\"#$%$&'()*+(&,+,-&-+,./&0,)123.\")4&)5-,5\"-6&\"4&7879!\"#=-&! &%?$'3%2&%/()! $21(,/! 34! @#0K! $%,)95$%<! $/+!(5?&'+&! &44&,/+! 3%! &,3+7+/&2+K! L(/&'! b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b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cde.!(%5!/'(%+13'/&5!/3!/-&!)(C3'(/3'7!L$/-$%!Vc!-39'+!43'!+9C+&b9&%/!1-7+$,3,-&2$,()!(%5!<&3,-&2$,()!,-('(,/&'$E(/$3%H! M%A+$/9!1-7+$,3,-&2$,()!,-('(,/&'$E(/$3%!34!/-&!@#0!L(+!1&'43'2&5!9+$%<!(%!@b9(!=*ZPP! f\\\\! 29)/$1('(2&/&'! +3%5&! /3! 2&(+9'&! S&7!$%&%'(()'*+,+-&.'+.&%+/&-0)&1+0-'%++2)34-5%+0-'-'(+6%)7%8+9):)'(+;+-&.'+.&%+/&-0)&1+0-'%+2)34-5%+0-'-'(+6%)7%8+9%&)<+,+4-'+.&%+/&-0)&1+0-'%+2)34-5%+0-'-'(+6%)7%8+.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7301

1('(2&/&'+K! $%,)95$%<! 1OK! &)&,/'$,()! ,3%59,/$?$/7! I;.JK!3N$5(/$3%A'&59,/$3%!13/&%/$()!IZ*:JK!(%5!5$++3)?&5!3N7<&%!I0ZJ! (+! +-3L%! $%! 8$<HWH! :'$3'! /3! (%()7+$+K! /-&! @#0!+(21)&+! L&'&! 4$)/&'&5! /3! '&23?&! +9+1&%5&5! +3)$5+! (%5!(,$5$4$&5! L$/-! L$/-! V! L/H! ^! %$/'$,! (,$5! IOgZhJ! $%!(,,3'5(%,&! L$/-! /-&! 2(/'$N! +1&,$4$,(/$3%+! 34! ,&'/$4$&5!'&4&'&%,&! 2(/&'$()+! I.*#+J! 43'!! *;;+! (%5! 2(G3'! 2&/()+H!B/(%5('5! +3)9/$3%+! 4'32! :&'S$%! ;)2&'! (%5! .H:H@H! .-&2!L&'&! 9+&5! /3! &%+9'&! (%()7/$,()! (,,9'(,7! (%5! 2&/-35!?()$5(/$3%H! B9C+&b9&%/! b9(%/$4$,(/$3%! 34! *;;+! (%5! 3/-&'!2(G3'! 2&/()+! L(+! ,(''$&5! 39/! 9+$%<! C3/-!! :&'S$%;)2&'!g&NMZg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b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iA'(7! 5$44'(,/$3%! Ii*0J! (%()7+$+! /3! &%+9'&!-323<&%&$/7! (%5! '&1'&+&%/(/$?&! 1-(+&! $5&%/$4$,(/$3%H!#$%&'()3<$,()! ,-('(,/&'$E(/$3%! L(+! ,(''$&5! 39/! 9+$%<! (!Y'9S&'!0]!@5?(%,&!iA'(7!5$44'(,/32&/&'K!31&'(/$%<!3?&'!(!Vj! '(%<&! 34! \"\\e! /3! X\\eK! L$/-! (! +/&1! +$E&! 34! \"H\\e! (%5! (!,39%/$%<! /$2&! 34! c\\\"!+&,3%5+! 1&'!+/&1! /3! &%-(%,&!+$<%()!'&+3)9/$3%H! :-(+&! $5&%/$4$,(/$3%! L(+! 1&'43'2&5! 9+$%<! /-&!0$44'(,/! :)9+! ;?()9(/$3%! V\\\\i! +34/L('&! +9$/&K! L$/-!'&4&'&%,&! /3! /-&! :08Ac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b9&39+!1-(+&!(+!5&/($)&5!$%!=(C)&!WH\"H!@+*(-& 9$%& 0,->-4.>& ./-& \"4A>\".2& 0/B>\"3)3/-?\"3+(&3/+,+3.-,\"C+.\")4& );& <:=& +3,)>>& ./-& ./,--& \"45->.\"#+.-1& ?\"4\"4#&+,-+>$&;)&2&%/()! (%()7+$+! 34! @#0! 4'32! /-'&&! +&)&,/&5!2$%$%<!+$/&+!'&?&()&5!?('7$%<!,3%,&%/'(/$3%+!34!*;;+K!L$/-!/-&!-$<-&+/!)&?&)+!3C+&'?&5!$%!@#0!(++3,$(/&5!L$/-!/$%!3'&!5&13+$/+H! =(C)&! WHV! +-3L+! /-(/! @#0! 4'32! /-&! /$%! 3'&!5&13+$/! $%! :&'(S! ,3%/($%+! \"UH]c! 2<kP! 34! *;;+K! L-$,-! $+!8QLW 6LWH $ 6LWH% 6LWH &@B0-&);&),-& A .\"4 \",)4& \",)4&D+?0(-&),\"#\"4& E-,+F @-,-4##+42& E+/+4#&0G& A 7$H7 9$97& 9$87&I(-3.,\"3+(&J)4123\"5\".B&KIJL&MDN3?& 7OH9$%9& 7%PH$7Q& %%RH$O8&@-?0-,+.2,-& SJ& 7Q$9& 7Q$O& 9%$%&TU\"1+.\")4&,-123.\")4&0).-4.\"+(&KTVEL&?W& O9%$P8& 9PX$%9& PP8$Q9&=\">>)(5-1&)UB#-4& ?#NY& O$%8& O$8X& O$HP&.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(73023DUDPHWHU

-$<-&'!/-(%!/-&! VHWV!2<kP! (%5! \"Hc\\!2<kP! 439%5!$%!@#0!4'32! $'3%! 3'&! 5&13+$/+! $%! =&'&%<<(%9! (%5!:(-(%<!'&+1&,/$?&)7H! =-&! 23C$)$/7! 34! *;;+! $%! @#0! $++/'3%<)7!$%4)9&%,&5!C7!/-&!1O!34!/-&!(b9&39+!+3)9/$3%H!@+!'&13'/&5! C7! 1'&?$39+! +/957#!\"$K! (%! $%?&'+&!'&)(/$3%+-$1! &N$+/+! C&/L&&%! 1O! (%5! 5$++3)?&5! *;;+!,3%,&%/'(/$3%+K! L-&'&!)3L&'!1O!,3%5$/$3%+!&%-(%,&!*;;+!+3)9C$)$/7!(%5!23C$)$/7!$%!+3)9/$3%H!@+*(-&9$7&VII>&+41&)./-,&?+Z),&?-.+(&3)43-4.,+.\")4&K?#NYL&\"4&<:=&);&./,--&\"45->.\"#+.-1&?\"4\"4#&+,-+>&[ 4$1$&\\&4).&1-.-3.+*(-*HQHUDWLRQRI5((V(QULFKHG3UHFLSLWDWH*;;+A&%'$,-&5!1'&,$1$/(/&+!L&'&!<&%&'(/&5!4'32!'(L!@#0!(4/&'! +&b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i*0! (%()7+$+! ,3%4$'2&5! /-&! 1'&+&%,&! 34! *;;+AC&('$%<! 1-(+&+! $%,)95$%<! )(%/-(%92! 3N$5&K! ,&'$92! 3N$5&K!7//'$92! 3N$5&! (%5! 1'(+&3572$92! 3N$5&! $%! /-&! *;;+A&%'$,-&5!1'&,$1$/(/&!(+!+-3L%!$%!8$<H!cH!=-&!*;;+A&%'$,-&5!1'&,$1$/(/&! ()+3! &N-$C$/+! (%! (23'1-39+! 1-(+&! $%5$,(/$%<!)3L&'! +/'9,/9'()! +/(C$)$/7! (%5! <'&(/&'! +9$/(C$)$/7! 43'!-75'32&/())9'<$,()! 1'3,&++$%<! 1('/$,9)(')7! $%! /&'2+! 34!)&(,-(C$)$/7H!!\"#$P$&E+..-,4&);&]V=&;),&VII>A-4,\"3/-1&0,-3\"0\".+.-5HFRYHU\\RI5DUH(DUWK2[DODWH:9'$4$,(/$3%! 34! *;;+! 4'32! /-&! *;;+A&%'$,-&5! 1'&,$1$/(/&!L(+! ,(''$&5! 39/! /-'39<-! '&5$++3)9/$3%! 43))3L&5! C7! 3N()$,!(,$5!1'&,$1$/(/$3%H!@%!O_BZl!,3%,&%/'(/$3%!34!T!#!L$/-!(!+3)$5A/3A)$b9$5!'(/$3!IBkPJ!34!VT!<kP!(,-$&?&5!31/$2()!*;;+!'&,3?&'7! 34! ]U^H! 8$<H! TH! +-3L+! /-&! '&5$++3)9/$3%!&N1&'$2&%/! ,3%59,/&5! 3?&'! \"V\\! 2$%9/&+H! *;;+! '&,3?&'7!1)(/&(9+!(4/&'!X\\!2$%9/&+K!$%5$,(/$%<!/-(/!)&(,-$%<!S$%&/$,+!'&(,-! &b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ffl5(92/86,'$7$'$1,129$6,79(7303

/-&! 1'&,$1$/(/$3%! 34!*;;+! 3N()(/&+!L$/-!(! 19'$/7! 34! WUmcV!L/H^! (+! +-3L%! $%! 8$<HfH! =-&! ,3%+$+/&%/! '&,3?&'7!(,'3++! '&1)$,(/&! /'$()+! 5&23%+/'(/&+! /-&!'3C9+/%&++! (%5!'&1'359,$C$)$/7!34!/-&!&N/'(,/$3%!1'3,&++H!=-&!*;;+!3N()(/&!19'$/7!(,-$&?&5!5&23%+/'(/&+!1'32$+$%<!5&?&)312&%/!+$%,&!$%59+/'$()!+&2$A1'359,/!<'(5&+!/71$,())7!'&b9$'&! c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5()(5(1&(6-RXUQDO`%a =2..+b&@$b&c\"?b&c$&G$b&d3/\"?\"B+b&:$b&c6)4b&I$&I$b&e-)4b&_$G$b&=--0b&<$b&f&g24b&D$&@$& K78%XL$&'()*+(&1-?+41& ;),& ,+,--+,./& ,->)2,3->& +41& >.,+.-#\"->& ;),& #,--4& ?\"4\"4#$I45\",)4?-4.+(&V->-+,3/b&%H8b&%Q7\\%R8$`7a Y\"2b& D$& Y$b& !+4b& G$& V$b& Y\"2b& ]$b& :-4#b& e$b& _2.3/-,b& <$& V$bg+44b&Y$b&g+4#b&c$&!$b&f&Y\"b&]$&J$&K7879L$&'()*+(&,+,-&-+,./-(-?-4.>& 0,)Z-3.>^& h-6& 1-5-()0?-4.>& +41& >200(B& 3/+\"4>$T,-&'-)()#B&V-5\"-6>b&%HOK<0,\"(Lb&%8HP7Q$`9a =\"+(()b&D$b&@,+4b&Y$&G$b&Y+,\"5\"i,-b&=$b&f&_(+\">b& e$&!$& K787HL$Y-+3/\"4#& +41& ,-3)5-,B& );& ,+,-& -+,./& -(-?-4.>b& 3)00-,b4\"3F-(b&>\"(5-,&+41&#)(1&;,)?&2>-1&>?+,.0/)4-&3\",32\".&*)+,1>$:\"4-,+(>&I4#\"4--,\"4#b&777KD-0.-?*-,&787PL$`Pa :)F)-4+b& _$& c$b& :)F/+/(+4-b& Y$& D$b& f& J(+,F-b& D$&K7877L$I;;-3.>& );& +3\"1& 3)43-4.,+.\")4& )4& ./-& ,-3)5-,B& );& ,+,-& -+,./-(-?-4.>& ;,)?& 3)+(& ;(B& +>/$& j4.-,4+.\")4+(& e)2,4+(& );& J)+('-)()#Bb&7HRK:+BL$`Ha _),,+b&J$&V$b&E)4.\"F->b&g$b&_\"44-?+4>b&c$b&f&W+4&'-,5-4b&@$K78%HL$& Y-+3/\"4#& );& ,+,-& -+,./>& ;,)?& *+2U\".-& ,->\"12-& K,-1?21L$&:\"4-,+(>&I4#\"4--,\"4#b&OXb&78\\7O$`Xa <B),+b& J$b& :+3k+>b& !$b& @),,->b& I$b& f& h\"-.)b& e$& :$& K78%HL$V+,-&I+,./&I(-?-4.>&\"4&<3\"1&:\"4-&=,+\"4+#-$&78%XK%Lb&%\\77$`Oa G-,?+>>\"b&:$b&',+4+1)>b&:$b&W+(1-,,+?+b&J$b&<B),+b&J$b&fJ),.\"4+b&e$&Y$&K787%L$&V-3)5-,B&);&V+,-&I+,./&I(-?-4.>&;,)?+3\"1\"3& ?\"4-& 6+.-,>& *B& \"4.-#,+.\")4& );& +& >-(-3.\"5-& 3/-(+.\"4#\")4A-U3/+4#-,& +41& +& >)(5-4.& \"?0,-#4+.-1& ,->\"4$& e)2,4+(& );I45\",)4?-4.+(&J/-?\"3+(&I4#\"4--,\"4#b&RKHLb&%8HR8X$`Qa l/+4#b&m$b& f& G)4+F-,b& V$& n$& K78%QL$& V+,-& -+,./& -(-?-4.>,-3)5-,B& 2>\"4#& >.+#-1& 0,-3\"0\".+.\")4& ;,)?& +& (-+3/+.-#-4-,+.-1& ;,)?& 3)+,>-& 3)+(& ,-;2>-$& j4.-,4+.\")4+(& e)2,4+(& );J)+(&'-)()#Bb&%RHb&%QR\\%RR$`Ra =\"+)b& G$b& g+4#b& G$b& @+4b& @$b& V-4b& '$b& g)2b& :$b& m2b& Y$bg+4#b&:$b&_+\"b&g$b&]\"+b&D$b&D)4#b&D$b&n2\"4.+4+b&:$b&Y\"2b&Y$bf& ]2-b& n$& K787PL$& h+5\"#+.\"4#& ./-& ,+,-& -+,./& -(-?-4.>(+41>3+0-^& J/+((-4#->b& \"44)5+.\")4>b& +41& >2>.+\"4+*\"(\".B$:\"4-,+(>&I4#\"4--,\"4#b&7%XK<2#2>.Lb&%8QQQR$`%8a DF)2>-4b& e$& '$b& l\"-?F\"-6\"3Cb& E$& !$b& f& :3=)4+(1b& Y$& :$K78%RL$& <3\"1& ?\"4-& 1,+\"4+#-& ;),?+.\")4b& 3)4.,)(& +41.,-+.?-4.^& <00,)+3/->& +41& >.,+.-#\"->$& IU.,+3.\"5-& j412>.,\"->+41&D)3\"-.Bb&XK%Lb&7P%\\7PR$`%%a D/+,\";b& :$& l$& :$b& V)C\"b& :$& D$& :$b& f& j*,+/\"?b& j$& K787PL$V-3)5-,B& );& ,+,-& -+,./& -(-?-4.& ;,)?& :+(+B>\"+4& +3\"1& ?\"4-1,+\"4+#-$&<jE&J)4;-,-43-&E,)3--1\"4#>b&98%PK%L$`%7a V)B-,AY+5+((o-b&<$b&h-32(\".+b&J$&:$b&f&J)21-,.b&Y$& K7878L$V-?)5+(&+41&0).-4.\"+(&,-3)5-,B&);&,+,-&-+,./&-(-?-4.>&;,)??\"4-& 6+.-,$& e)2,4+(& );& j412>.,\"+(& +41& I4#\"4--,\"4#J/-?\">.,Bb&QRb&PO\\HO$.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7304

Granite-Enhanced Basalt Composites: Shaping the Next Generation of Automotive Structures 0RKDPDG $VURIL0XVOLP$LGDK-XPDKDW6KDKUXO$]DP$EGXOODK0RFKDPDG&KDOLG0RKG $]UXO-DDIDU DQG 5D\\PRQG6LHZ7HQJ /R\\1Kuala Lumpur Industrial Training Institute, Jalan Kuchai Lama, Kuala Lumpur, Malaysia 2Faculty of Mechanical Engineering, University Technology MARA, Shah Alam, Selangor, Malaysia 3Department of Metallurgical and Material Engineering, Kampus Baru UI, Universitas Indonesia, Depok, Indonesia 4Centre for Instructor and Advanced Skill Training, Jalan Petani 19/1, Shah Alam, Selangor, Malaysia 5CTG Sdn Bhd, PT-1361, Jalan Kesidang 5, Kampung Sungai Choh, 48000 Rawang Selangor, Malaysia Corresponding email: [email protected]$EVWUDFWffl Granite waste, a byproduct of quarrying and stone-cutting industries, poses significantenvironmental challenges due to improper disposal practices that contribute to soil and water pollution, land degradation, and air quality issues. In recent years, researchers have explored its potential valorisation in various engineering applications, particularly in composite material development, as a sustainable alternative to conventional fillers and reinforcements. The increasing demand for lightweight, durable, and highperformance materials in the automotive industry has spurred the exploration of advanced composite materials. This study investigates the mechanical performance of basalt fibre-reinforced polymer (BFRP) and glass fibre-reinforced polymer (GFRP) composites enhanced with nano-silica particles extracted from granite dust, for potential application in automotive structures, particularly truck body panels. The composites were fabricated using a hand lay-up and vacuum silicon mould process, with varying nano-silica concentrations (0ñ5 wt%). Mechanical characterisation was conducted through tensile, flexural, and compressive tests according to ASTM standards. The results revealed that the inclusion of 1 wt% nano-silica significantly improved the tensile, flexural, and compressive properties across all composite types, with BFRP achieving the highest tensile strength of 337.67 MPa (an increase of 7.4%), and GFRP reaching a 25% increase in tensile performance. Higher nano-silica loadings beyond 1 wt% led to agglomeration and reduced performance. Comparisons with industrial samples indicated that the optimised composites outperformed conventional materials, showcasing remarkable gainsóup to 487% improvement in tensile strength for BFRP. These findings suggest that nano-silica-modified basalt composites offer a promising pathway for developing highperformance, lightweight, and sustainable materials in the automotive industry.. .H\\ZRUGVffl nano silica; basalt fibre; glass fibre; polyester; vacuum silicon mould;polymer composite ,1752'8&7,21Granite is extensively utilised globally in construction and architecture as an ornamental substance. The material is highly regarded due to its exceptional durability, pleasing aesthetic qualities, and notable resistance to both heat and scratches. Nevertheless, using granite raises certain apprehensions about its environmental implications, including its impact on the ecosystem, habitat degradation, soil erosion, water contamination, and potential health hazards. Although granite presents various advantages, it is crucial to carefully consider its environmental impact, health implications, labour conditions, and long-term sustainability factors to achieve a balanced approach to its utilisation [1]. Basalt fibre is a multifaceted substance obtained from naturally occurring volcanic rock known as basalt. The material possesses distinct characteristics that make it suitable for various applications on a global scale, particularly in the Automotive and Aerospace industries [2], [3]. These properties enable the material to effectively reduce weight without compromising its strength[4]. Automobile components such as body panels, interior parts, and structural elements find application in various automotive contexts [5].The utilisation of basalt fibre globally is progressively expanding due to its inherent benefits, including its notable tensile strength, fire resistance, and resistance to chemicals and corrosion[5], [6]. The sustainability, ample availability, and minimal environmental footprint relative .219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7305

to alternative fibres render it a compelling option across multiple industries [7]. Nano silica, called silica nanoparticles or colloidal silica, is a silicon dioxide variant characterised by particle dimensions falling within the nanometer scale [8]. The material possesses distinct characteristics that render it suitable for various industrial applications, including its use as a rubber and plastics reinforcing agent [9]. Incorporating nano silica particles has been shown to positively impact the mechanical characteristics of rubber and plastic materials, improving their strength, stiffness, and durability [10].  0$7(5,$/6$1'0(7+2'6Industrial polyester resin and Hardener M60 Butanox was supplied by Carbon Tech Global Sdn; meanwhile, woven glass fibre and basalt fibre were supplied by Innovative Poltrusion Sdn Bhd. Nano silica was extracted from granite dust which has been supplied by JKR Malaysia.2.1 Composite Fabrications Process The fibre-reinforced composites were prepared using a hand lay-up and vacuum silicon mould in which supplied by CTG SD.BHD, The polyester resin was mixed with a hardener in a ratio of 100:2 by weight, recommended by the supplier, to ensure the resin was fully cured 2.2 ExperimentalTwelve system sample sizes of 300 x 300 mm were prepared and cut, following ASTM-D3039 for tensile, ASTM-D790 for flexural, and ASTM D3410 for compression. Each system was designed with five identical samples.2.3 Tensile Strength Measurements In the case of BFRC and GFRC composites, the ASTM D-3039 standard was used for conducting tensile testing. The SHIMADZU 3366 machine was used for testing, and the specimen used for tensile testing has the following dimensions: Length of 250mm, width of 25mm, thickness of 2mm, and gauge length (distance between the grips) of 50mm. The crosshead speed for the tensile test is set at 5mm/min, which is the rate at which the grips move apart during the trial. A standard sample size of five specimens was used in most testing methodologies to ensure statistical validity and to reduce any outliers' impact [9]. The tensile strength and elongation were calculated of the Basalt Fibre Reinforced composite (BFRC), Glass Fibre Reinforced Composite (GFRC) and Polyester (PE) resin.2.4 Flexural Properties MeasurementsA standard test procedure used to ascertain the flexural properties of composites is ASTM D790-03. In the test, a rectangular specimen was bent until it fractures, and the force and displacement are recorded. The recorded data used to determine flexural strength (FS) and flexural modulus (FM). The Shimadzu 3366-10kN machine, wasused to test the materials' mechanical properties. In this specific test, the samples were rectangular and had dimensions of 80 mm (length) x 13 mm (width) x 5 mm (thickness). The test was conducted at a crosshead speed of 2 mm/min, the rate at which the machine's crosshead moves during the trial. At least five samples were prepared for each formulation, which refers to the specific composition and processing conditions used to produce the material [10]. 2.5 Compression MeasurementsComposite materials are widely used in various industries due to their exceptional strength-to-weight ratio. The ASTM D3410 standard provides a comprehensive protocol to assess these materials' compressive properties. This compression test method is outlined in ASTM D3410 for composite materials with dimensions 110mm length, 10mm width, and 2mm thickness. Following the specified dimensions and test protocol can accurately assess the material's compressive strength, modulus, and deformation behaviour. This information is crucial for designing and selecting composite materials in various applications where compression forces may be encountered. Understanding the behaviour of composite materials under compression is essential for ensuring structural integrity and overall performance in real-world scenarios [11]. 5(68/76 $1' ',6&866,21The results are the mean values of five samples tested for each type of composite laminate. The difference in the sample is the weight percentage of nano silica mixed in the resin before the pouring process during the hand lay-up fabrication process. The tensile, flexural, and compression properties of composite laminates, PE, BFRC, and GFRC were analysed. The findings thoroughly discussed the effect of different characters.1. Effect of nano silica on polyester composite.2. Effect of nano silica on Basalt Fibre ReinforcedComposite.3. Effect of nano silica on Glass Fibre ReinforcedComposite; and4. Effect of nano silica on BFRC and GFRCCompared to Industrial Sample3.1 Effect of nano silica on Polyester CompositeThe polyester composite's tensile, flexural, and compressive strengths are shown in Fig.1. The result shows that the highest tensile value is 1 wt% with 62.97MPa compared to 57.46MPa at the unmodified polyester .219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7306

compositeóthe improvement of 9.5% increases when nano silica is incorporated in polyester resin. In 3wt%, the value decreased to 54.40MPa and continued to decrease to 48.59MPa in 5wt% of nano silica. Nano silica tends to agglomerate when 3 wt% or more powders are added [12], [13]. The flexural value for unmodified PE is 88.10 MPa, and 105.10 MPa at 1 wt% containing nano silica, with an increasing value of 19.3%. The value continuously decreased to 88.46MPa and 83.92MPa.)LJXUH7HQVLOHIOH[XUDODQGFRPSUHVVLRQVWUHQJWKRI3RO\\HVWHU&RPSRVLWHThe compressive strength value also increased from 86.67MPa to 94.70MPa, with an increasing percentage of 9.27% at 1 wt% containing nano silica. However, incorporation of nano silica leads to a decrease in the value of compressive strength to 90.61MPa and 89.14MPa at 3wt% and 5wt%. The experimental findings indicate that incorporating nano-silica in polyester composites resulted in a notable improvement in the mechanical properties, specifically tensile, flexural, and compressive strength [14], [15], [16]. The observed enhancements ranged from 9% to 25%. The rationale behind utilising nano-silica in this context is attributed to its expansive surface area, which enables it to effectively occupy the voids within the polyester material up to a specific weight percentage [17]. In the present experiment, it can be concluded that the optimal weight percentage deemed appropriate is 1 wt%. [18].3.2 Effect of nano-silica on Basalt Fibre Reinforced Composite (BFRC)The tensile, flexural, and compressive properties of the BFRC composite are shown in Fig.2. Based on the results, the highest tensile value is in 1 wt%, with 337.67MPa increasing from 314.43MPa at unmodified BFRC. The percentage improved by 7.4% when polyester resin was incorporated with nano silica. In 3wt%, the value continuously decreases to 300.65 and 275.42 in 5wt% of nano silica. )LJXUH. 7HQVLOH)OH[XUDODQGFRPSUHVVLYHVWUHQJWK%)5&The flexural value exhibited a significant increase of 17.5%, ranging from 244.20MPa to 286.86MPa. Subsequently, the value exhibited a consistent downward trend, reaching magnitudes of 268.79MPa and 258.07MPa. The compressive strength value exhibited a notable increase, rising from 125.76MPa to 153.88MPa, representing a percentage increase of 22.4%. At a weight percentage of 5%, the value decreases to 128.97MPa and 106.21MPa. Incorporating nano-silica into polyester composites resulted in a variation in tensile, flexural, and compressive strength properties [19], [20], ranging from 7% to 22.4%. The reason for this phenomenon is attributed to the expansive surface area of nano-silica particles, which enables them to effectively occupy the available space within the polyester matrix up to a specific weight percentage (wt.%), as observed in this experimental study, where the saturation point was determined to be 1 wt%.[21].3.3 Effect of nano-silica on Glass Fibre Reinforced Composite (GFRC)The tensile, flexural, and compressive properties of the GFRC composite are shown in Fig.3. The highest tensile value is 1 wt% with 306.37MPa compared to 244.98MPa at unmodified GFRC. The value is increased by 25% while nano silica is incorporated in the polyester resin. In 3wt%, the value decreased to 276.93MPa and further decreased to 206.17 in 5wt% of nano silica. The flexural value went from 223.64MPa to 249.19MPa, with an increasing value of 11.4%. After that, the value continuously decreased to 238.03MPa and 224.03MPa. The compressive strength value also increased from 99.78MPa to 114.50MPa with an increasing percentage of 14.75%. The value decreases to 113.36MPa and 96.79MPa at 5wt%..219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7307

Introducing nano-silica into polyester composites had a notable impact on the mechanical properties, encompassing tensile, flexural, and compressive strength, with enhancements ranging from a substantial 11.4% to a remarkable 25%. This impressive variation underscores the profound influence of nano-silica on the composite's performance [22]. The rationale for including nano-silica in this study hinges on its exceptional characteristics, primarily its expansive surface area [6]. This unique attribute facilitates its seamless integration into the polyester matrix, particularly within a narrow weight percentage range, specifically at the optimum concentration of 1 wt%. This precise balance ensures the effective utilisation of nano-silica's inherent properties to augment the composite's strength, making it a pivotal element in the pursuit of advanced materials engineering [23].)LJXUH7HQVLOHIOH[XUDODQGFRPSUHVVLYHVWUHQJWKRI*)5&3.4 Effect of nano-silica on BFRC and GFRC Compared to Industrial SampleFig.4 displays the graphical representation of tensile properties and offers a compelling comparison between the industrial sample and the peak strength values attained by PE, BFRC, and GFRC. Among these materials, BFRC stands out as the frontrunner, boasting the highest tensile strength value, which reaches an impressive 337.67 MPa when enriched with 1 wt% nano-silica. In stark contrast, the PE sample occupies the lower end of the spectrum, registering a comparatively modest strength of 62.97 MPa. The industrial sample, CTG at 1 wt%, occupies the middle ground with a tensile strength of 91.79 MPa. Meanwhile, the GFRC sample, also with 1 wt% nano-silica, surges ahead with a remarkable tensile strength of 306.37 MPa. The transformative impact of nano-silica on these materials is striking. For instance, the tensile strength of PE exhibits a staggering percentage increase of 433%, showcasing the material's newfound resilience. BFRC, on the other hand, witnesses an even more remarkable percentage increase of 487.6%, emphasising the substantial potential for enhancement that nano-silica brings to the table. These results illuminate the immense promise of nano-silica in revolutionising the tensile properties of these materials, paving the way for groundbreaking advances in various applications [16], [24].)LJXUH)OH[XUDO6WUHQJWK&RPSDULVRQPD[LPXPZWZLWKLQGXVWULDOVDPSOHThe flexural strength, with the comparison between the industrial sample and the highest value of the strength of PE, BFRC, and GFRC, is shown in Fig.5. The results of our experimentation reveal compelling improvements in flexural strength when incorporating 1wt% nano-silica into various composite samples. In particular, the CTG sample demonstrated a flexural strength of 117.37 MPa, while the GFRP sample showcased a remarkable increase to 249.19 MPa. This represents a substantial 45% enhancement attributed to the introduction of nano-silica. Moreover, our investigations continued to yield promising outcomes as we expanded our focus. The flexural strength values continued to exhibit a consistent upward trajectory, culminating in values reaching as high as 286.86 MPa for 1 wt% BFRC,signifying an impressive 67.4% increase. These findings underscore the significant potential of nano-silica as a key component in optimising the mechanical properties of composite materials [25], [26], offering exciting prospects for advanced material engineering.)LJXUH)OH[XUDO6WUHQJWK&RPSDULVRQPD[LPXPZWZLWKLQGXVWULDOVDPSOH.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7308

Based on Fig.6, the progression of compressive strength values with the incorporation of nano-silica is quite remarkable. Initially, it has been observed an 8% increase was observed as the value climbed from 105.71 MPa to 114.50 MPa. However, this uptrend continued to intensify, reaching a peak at an astounding 153.88 MPa for BFRC, marking a substantial 45% increment. These findings underscore the impressive potential of nano-silica to enhance the compressive strength of materials, opening doors to innovative applications in various industries [27], [28].)LJXUH&RPSUHVVLRQVWUHQJWKRIGLIIHUHQWZWQDQRVLOLFD &21&/86,21The integration of nano-silica presents a promising avenue for enhancing the mechanical properties of various materials, including Polyester (PE), Basalt Fibre Reinforced Composite (BFRC), and Glass FiberReinforced Composite (GFRC). The addition of nanosilica has been shown to significantly augment these materials' tensile, flexural, and compression strength. It's worth noting that nano-silica tends to agglomerate at specific weight percentages, indicating an optimal concentration of 1 wt%. To pave the way for future research endeavors, there is considerable room for improvement in the preparation of nano-silica during the resin mixing process. One potential enhancement is using a vacuum chamber in conjunction with stirring techniques. This approach can help mitigate agglomeration issues and ensure a more uniform dispersion of nano-silica within the resin matrix. The outstanding mechanical properties exhibited by these newly developed composites surpass those of traditional industrial samples. This breakthrough makes them exceptionally well-suited for a wide range of industrial applications, including but not limited to truck body panels and various related accessories. As the research in this field advances, anticipate even more excellent opportunities for innovation and improvement in industrial materials and components.1. Akil, H., Zamri, M. H., & Osman, M. R.(2015). The use of kenaf fibers asreinforcements in composites. In Biofiberreinforcements in composite materials (pp.138-161). Woodhead Publishing.2. Bediwy, A., & El-Salakawy, E. F. (2021).Mechanical properties of hybrid structuresincorporating nano-silica and basalt fiberpellets. CivilEng, 2(4), 909-928.3. Chakartnarodom, P., Prakaypan, W., Ineure,P., Chuankrerkkul, N., Laitila, E. A., &Kongkajun, N. (2020). Properties andperformance of the basalt-fiber reinforcedtexture roof tiles. Case Studies inConstruction Materials, 13, e00444.4. Chee, S. S., Jawaid, M., Alothman, O. Y., &Fouad, H. (2021). Effects of nanoclay onmechanical and dynamic mechanicalproperties of bamboo/kenaf reinforced epoxyhybrid composites. Polymers, 13(3), 395.5. D'Mello, J., D'Souza, A. G., Gowda, S. H., &Pinto, D. (2019, March). Experimentalinvestigation of compression, flexuralstrength and damping behaviour of graniteparticulate epoxy matrix composite. In AIPConference Proceedings (Vol. 2080, No. 1).AIP Publishing.6. Mohammad, N.E., & Jumahat, A. (2019).Effects of Kenaf and Basalt FacesheetsModified Nanosilica of Closed CellAluminium Sandwich Panel. InternationalJournal of Recent Technology andEngineering (IJRTE), Volume-8 Issue-4,November 2019.7. ERKL !,\" A.,\" BOZKURT,\" ÷.\" Y.,\" &\" ALTEKREETI, W. F. (2022). Influence ofNano-Silica on the Mechanical Properties ofJute/Glass Fiber Reinforced Epoxy HybridComposites. «ukurova ‹niversitesiM¸hendislik Fak¸ltesi Dergisi, 37(2), 399-410.8. Farouk, M., Soltan, A., Schl¸ter, S.,Hamzawy, E., Farrag, A., El-Kammar, A., ...& Pollmann, H. (2021). Optimisation ofmicrostructure of basalt-based fibers intendedfor improved thermal and acousticinsulations. Journal of Building Engineering,34, 101904. 9. Fathy, A., Shaker, A., Hamid, M. A., &Megahed, A. A. (2017). The effects of nanosilica/nano-alumina on fatigue behavior ofglass fiber-reinforced epoxy composites.Journal of Composite Materials, 51(12),1667-1679.10. Jena, A., Prusty, R. K., & Ray, B. C. (2020).Mechanical and thermal behaviour of multi-.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(73095()(5(1&(6

layer graphene and nanosilica reinforced glass Fiber/Epoxy composites. Materials Today: Proceedings, 33, 5184-5189.11. Jumahat, A., Soutis, C., Jones, F. R., &Hodzic, A. (2010). Effect of silicananoparticles on compressive properties of anepoxy polymer. Journal of Materials Science,45, 5973-5983.12. Kaka, D., Fatah, R. A., Gharib, P., &Mustafa, A. (2021). Mechanical Properties ofPolyester Toughened with Nano-Silica. IraqiJournal of Industrial Research, 8(3), 61-68.13. Khan, K., Ahmad, W., Amin, M. N., &Nazar, S. (2022). Nano-silica-modifiedconcrete: A bibliographic analysis andcomprehensive review of material properties.Nanomaterials, 12(12), 1989.14. Kumar, P. K., & Kumar, B. N. (2022).Improvement of impact strength of novelintra-ply basalt/kevlar composite by additionof silica nanoparticles in comparison withbasalt/kevlar composite using resin transfermould process. Materials Today:Proceedings, 69, 843-847.15. Liu, D., Liu, R., Ping, S., Zhang, S., & Liu,G. (2023). Cyclic thermoresistivity of resinbased carbon fiber bars modified with mixedcarbon powder and nano-silica. MaterialsResearch Express, 10(2), 025601.16. Madhavi, P., Shekar, K. C., Poojith, K.,Kumar, P. S., Khan, P. U., & Gowtham, P. L.(2021, February). Flexural and Inter-LaminarShear Strength of Glass/Carbon FabricReinforced Composite. In IOP ConferenceSeries: Materials Science and Engineering(Vol. 1057, No. 1, p. 012016). IOPPublishing.17. Mahovi#\" Polja$ek,\" S.,\" Priselac,\" D.,Tomaöegovi#,\" T.,\" Elesini,\" U.\" S.,\" Leskovöek,M., & Leskovac, M. (2022). Effect of theAddition of Nano-Silica\" and\" Poly\" (%-caprolactone) on the Mechanical and ThermalProperties of Poly (lactic acid) Blends andPossible Application in Embossing Process.Polymers, 14(22), 4861.18. Pereira, M. L., F. da Silva, P., Fernandes, I.,& Chastre, C. (2021). Characterisation andcorrelation of engineering properties ofbasalts. Bulletin of Engineering Geology andthe Environment, 80, 2889-2910.19. Quadflieg, T., Srivastava, V. K., Gries, T., &Bhatt, S. (2023). Mechanical Performance ofHybrid Graphene Nanoplates, Fly-Ash,Cement, Silica, and Sand Particles FilledCross-Ply Carbon Fibre Woven FabricReinforced Epoxy Polymer CompositesBeam and Column. Journal of Materials Science Research, 12(1), 22-35.20. Raja Othman, R. N., Subramaniam, D. K.,Ezani, N. A., Abdullah, M. F., & Ku Ahmad,K. Z. (2022). The synergistic effects ofhybrid micro and nano silica in influencingthe mechanical properties of epoxycompositesóA new model. Polymers,14(19), 3969.21. Fong, T. C., Saba, N., Liew, C. K., De Silva,R., Hoque, M. E., & Goh, K. L. (2015). Yarnflax fibres for polymer-coated sutures andhand lay-up polymer composite laminates.Manufacturing of natural fibre reinforcedpolymer composites, 155-175.22. Saminathan, R., Hadidi, H., Fageehi, Y. A.,Manoj Kumar, P., Venkatasudhahar, M.,Ram, S., & Gebreyohannes, D. T. (2022).Experimental analysis of mechanical andthermal characteristics of luffa/epoxypolymer composite under the influence ofnanosilica. Advances in Materials Scienceand Engineering, 2022.23. Sapiai, N., Jumahat, A., Jawaid, M., Midani,M., & Khan, A. (2020). Tensile and flexuralproperties of silica nanoparticles modifiedunidirectional kenaf and hybrid glass/kenafepoxy composites. Polymers, 12(11), 2733.24. Sapiai, N., Jumahat, A., Manap, N., & Usoff,M. A. I. (2015). Effect of nanofillersdispersion on mechanical properties ofclay/epoxy and silica/epoxy nanocomposites.J. Teknol, 76, 107-111.25. Sari, Y. P., Dona, R., Hilmi, A. R., &Pratapa, S. (2023, May). Effects of samplethickness and filler composition on the tensilestrength and optical absorbance ofPMMA/nano-zircon composites. In AIPConference Proceedings (Vol. 2604, No. 1).AIP Publishing.26. Saroj, S., Nayak, S., & Jesthi, D. K. (2022).Effect of hybridisation ofcarbon/glass/flax/kenaf fibre composite onflexural and impact properties. MaterialsToday: Proceedings, 49, 502-506.27. Wu, Z., Wang, X., Liu, J., & Chen, X.(2020). Mineral fibres: basalt. In Handbookof Natural Fibres (pp. 433-502). WoodheadPublishing.28. Zhao, G., Cao, S., & Zhang, J. (2021). Studyon Distribution of Tensile Fatigue Life ofBasalt Fiber Composites. In IOP ConferenceSeries: Earth and Environmental Science(Vol. 639, No. 1, p. 012022)..219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7310

!\"#$%&'($()*%+,\"-'#)%($.+/'#0+123(.\"3%+!\"#$%&#$'#(#)#4.+.5\"26+7+89.:(\"2()*%+7*:%'2(:\"3%+:#+;*(.:\"-+,\"-'#)%($.+\"2+<\"=9\"$+8#(>++0RKG$GLO+DNDP%LQ2VPDQ0XKDPPDG/XTPDQ+DNLPL$EGXO$]LV +X]DLIDK.DPDUXO.KDOLG!#$%$&$'!()*'+,+-.!/.0.$!1$'!2$*$'$'!3+,.&)*'.*!(4'!56)1!7$8.9!56)1!:80$.,!;+99)8<+'1.'-!)0$.,=!$1.,><&8'?)14?06.H\\ZRUGVffl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`,0$@16! a!M%1),9$@0$'J!NKNZH?!!5.04,&$')+48,6J! 2$,$68.$! C$A)8! )A+,+-.A$,!A@$,,)'-)8! <+8)1! %6! .'D$8.D)! :*$'! F$'1$9$6$!GHI-$1+\"J',/0I01K! 8<?HJ! $! C9)8@T$&)9! 8<)A.)8! +9.-.'$,,6!.'&9+14A)1! C+9! $I4$9.40! A,)$'.'-?! (@).9! 4'A+'&9+,,)1!<9+,.C)9$&.+'!&@9)$&)'8!'$&.D)!$I4$&.A!)A+868&)08!Gb'--$'-!)&!$,?J!NKN\\H?!(49'.'-!&@.8!%.+,+-.A$,!T$8&)!.'&+!$!D$,4$%,)!9)8+49A)! C+9! 848&$.'$%,)! 0.A9+%)$18! 84<<+9&8! %+&@!.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7311$EVWUDFWffl7KLVVWXG\\SUHVHQWVDQHFRIULHQGO\\DSSURDFKWRDGGUHVVLQJPLFURSODVWLFSROOXWLRQDQGPDQDJLQJLQYDVLYHVSHFLHVE\\XWLOL]LQJWKHVNLQRI,NDQ%DQGDUD\\D3WHU\\JRSOLFKWK\\VVSDVDELRGHJUDGDEOHDOWHUQDWLYHWRV\\QWKHWLFPLFUREHDGVLQOLTXLGVRDS7KHILVKVNLQXQGHUJRHVDONDOLQHWUHDWPHQWGHJUHDVLQJJULQGLQJDQGLQFRUSRUDWLRQLQWRDQHXWUDOVRDSEDVH3DUWLFOHVL]HDQDO\\VLVDQGVHQVRU\\HYDOXDWLRQFRQILUPHGWKDWWKHUHVXOWLQJPLFUREHDGVUDQJLQJIURPWRȝPDUHVXLWDEOHIRUFRVPHWLFXVH$FRQFHQWUDWLRQSURYLGHGWKHPRVWIDYRUDEOHH[IROLDWLRQH[SHULHQFH7KHDEVHQFHRISDUWLFOHVVPDOOHUWKDQȝPLQGLFDWHVUHGXFHGHQYLURQPHQWDOULVN)XUWKHUUHVHDUFKDQGLQGXVWU\\FROODERUDWLRQDUHVWURQJO\\UHFRPPHQGHG

)A+,+-.A$,! 9)8&+9$&.+'! $'1! <+,,4&.+'! 9)14A&.+'! G5$9*$9! )&!$,?J!NKN\\H?!0$7(5,$/6$1'0(7+2'6!\"#$%&\"'()R.8@!8*.'! T$8!8+49A)1!C9+0!:*$'!F$'1$9$6$! .'! 5),$'-+9J!2$,$68.$?! 5+1.40! @619+P.1)! G7$cd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email protected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ffl!(@)!8*.'!T$8!&9)$&)1!T.&@!K?\"!28+1.40!@619+P.1)!G7$cdH!.'!$!\"=\"K!T).-@&B&+BD+,40)9$&.+!$&! Ze;! C+9! f! @+498!&+! 9)0+D)! +9-$'.A!.0<49.&.)8G^9$S$,)8BX$-4')8!)&!$,?J!NKN\\H?N? 'HJUHDVLQJ=!(@)!&9)$&)1!8*.'!T$8!&@)'!84%S)A&)1!&+!$1)-9)$8.'-!<9+A)88!48.'-!%4&$'+,!.'!$!\"=\"K!T).-@&B&+BD+,40)! 9$&.+! C+9!NZ!@+498!$&!Ze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g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hK! T)9)! 9)A+91)1J! 9)<9)8)'&.'-! &@)! <$9&.A,)! 8.E)8! $&!&@)! \"K&@J! QK&@J! $'1! h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cD)9$,,J!<$9&.A,)!8.E)!$'$,68.8!D$,.1$&)1!&@)! <@68.A$,! <9+<)9&.)8! +C!&@)!0.A9+%)$18! $'1! @.-@,.-@&)1!&@).9! <+&)'&.$,! $8! $! %.+1)-9$1$%,)! $'1! )'D.9+'0)'&$,,6!C9.)'1,6! $,&)9'$&.D)! &+! 86'&@)&.A! <,$8&.A! 0.A9+%)$18! .'!<)98+'$,!A$9)!<9+14A&8?!.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7312

5$-(,%4)67\"'8\"#&,-)(@9))! 8,.-@&,6! D$9.)1! C+904,$&.+'8! T)9)!1)D),+<)1J! $'1! <$9&.A.<$'&8! T)9)! $8*)1! &+! $88)88! &@)0!%$8)1! +'! 8A)'&J! &)P&49)J! $'1! +D)9$,,! $AA)<&$%.,.&6?! (@)!+%S)A&.D)!T$8!&+!4'1)98&$'1!-)')9$,!A+'840)9!<)9A)<&.+'[email protected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email protected]@)9! 8A+9)8!.'1.A$&)1!-9)$&)9!<9)C)9)'A)?!i@.,)! &@)! 8&416! A+,,)A&)1! 1$&$! +'! %+&@! 8A)'&! $'1!&)P&49)J!&@)! <9.0$96! C+A48! +C! &@)! $'$,68.8! T$8! +'!+D)9$,,!<9+14A&! $AA)<&$%.,.&6j$'! .'1.A$&+9! +C! A+'840)9!<49A@$8)! .'&)'&?! (@)! A+,,)A&)1! 1$&$! T)9)!$'$,6E)1! 48.'-!8&$&.8&.A$,!8+C&T$9)J!$'1! *)6! 1)8A9.<&.D)! 8&$&.8&.A8J! 84A@! $8!0)$'8! $'1! 8&$'1$91! 1)D.$&.+'8J!T)9)! A$,A4,$&)1?!R49&@)9! 8&$&.8&.A$,! &)8&.'-J!.'A,41.'-!$'$,68.8! +C! D$9.$'A)!GM7c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hB<+.'&!@)1+'.A! 8A$,)!Gk.$!)&!$,?J!NKNKH?!5(68/76(@)! -9$<@! \"?K! .,,48&9$&)8! &@)! A404,$&.D)! <)9A)'&$-)!1.8&9.%4&.+'! +C!0.A9+%)$18! %$8)1! +'! <$9&.A,)!8.E)J!9$'-.'-!C9+0! $<<9+P.0$&),6! K?\"! 0.A9+0)&)98! GL0H! &+! $8! ,$9-)! $8!\"KKK! L0?! MAA+91.'-! &+! &@)! 8&416! %6! dlW%$,+Dm! )&! $,?!GNKNKHJ! &@.8! %9+$1! 8.E)! 9$'-)! .'1.A$&)8! $! <+,61.8<)98)!868&)0J! 0)$'.'-! &@$&! &@)! 0.A9+%)$18! )P@.%.&! $! T.1)!1.8&9.%4&.+'! +C! <$9&.A,)!8.E)8?! (@.8! D$9.$&.+'! ,.*),6! 9)84,&8!C9+0! $! <9+14A&.+'! <9+A)88! &@$&! ,$A*8! 8&9.'-)'&!A+'&9+,J! ,)$1.'-!&+!$!@)&)9+-)')+48!0.P&49)!+C!<$9&.A,)!8.E)8!9$&@)9!&@$'!$!4'.C+90!+4&<4&?!(@)! 1$&$! 9)D)$,! &@$&! &@)! 0$S+9.&6! +C! &@)! 0.A9+%)$18! C$,,!T.&@.'!&@)!\"Kn\"KK!L0! 9$'-)J!$8!)D.1)'A)1!%6!&@)!<)$*!.'!&@)!-9$<@?!(@.8!8.E)!9$'-)!$,.-'8!T.&@!&6<.A$,!9)I4.9)0)'&8!C+9! A+80)&.A! $'1! 8*.'A$9)! $<<,.A$&.+'8J! T@)9)! -)'&,)!)PC+,.$&.+'! .8! <9)C)99)1?! d+T)D)9J! &@)! <9)8)'A)! +C! ,$9-)9!<$9&.A,)8j8+0)! 9)$A@.'-! 4<! &+! \"KKK! L0jC49&@)[email protected]@,.-@&8! &@)! T.1)! 8.E)! D$9.$%.,.&6! .'! &@)! 8$0<,)?! :'!A+'&9$8&J! 80$,,)9! <$9&.A,)8J! <$9&.A4,$9,6! &@+8)! 4'1)9! Q! L0J!$9)!$,0+8&!A+0<,)&),6!$%8)'&?!(@.8!$%8)'A)!84--)8&8!&@$&!$!8.)D.'-!8&)<!0$6!@$D)!%))'!.'A+9<+9$&)1!149.'-!<9+A)88.'-!&+! )PA,41)! C.')9! <$9&.A,)8J! 9)84,&.'-! .'! $! C.'$,! <9+14A&!A+0<+8)1!<9.0$9.,6!+C!0)1.40B!&+!,$9-)B8.E)1!0.A9+%)$18?!*UDSKffl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ffl5(92/86,'$7$'$1,129$6,79(7313

',6&866,21i@)'! A+0<$9)1! T.&@! A+00)9A.$,,6!<9+14A)1!0.A9+%)$18J! $! 1.8&.'A&! 1.CC)9)'A)! .'! 8.E)!4'.C+90.&6!%)A+0)8! $<<$9)'&?! ;+00)9A.$,! 0.A9+%)$18!$9)! &6<.A$,,6!0$'4C$A&49)1! 48.'-! <9)A.8)! 0)&@+18! 84A@!$8! -9.'1.'-! +9!<+,60)9.E$&.+'J! [email protected]@! $9)! 1)8.-')1! &+!<9+14A)! A+'8.8&)'&!<$9&.A,)!8.E)8!C+9!8<)A.C.A!$<<,.A$&.+'8!Gd4$'-!)&!$,?J!NKNNH?!R+9! .'8&$'A)J! A+80)&.A! 0.A9+%)$18!48)1! .'! )PC+,.$&.'-!8A94%8! .'! 2$,$68.$'! <9+14A&8! &6<.A$,,6! 9$'-)! C9+0! \"K!&+! \"op! L0! .'! 1.$0)&)9J! A,+8),6!9)8)0%,.'-! &@)! 8.E)!9$'-)! C+4'1! .'! &@.8! 8&416! Gd$%.%! )&! $,?J! NKNKH?!d+T)D)9J! 0.A9+%)$18!48)1! .'! .'148&9.$,! $<<,.A$&.+'8!+C&)'! 8<$'! $!%9+$1)9!9$'-)J! 1)<)'1.'-! +'! &@).9! .'&)'1)1!C4'A&.+'J! 84A@! $8!C.,&9$&.+'! +9! <+,.8@.'-?! i@.,)! &@)!C.8@! 8*.'B1)9.D)1!0.A9+%)$18! .'! &@.8! 8&416! 8@$9)! 8.0.,$9!8.E)!A@$9$A&)9.8&.A8! T.&@! A+00)9A.$,! <9+14A&8J! &@).9!%9+$1)9! 8.E)! 1.8&9.%4&.+'! $'1! <9)8)'A)! +C! ,$9-)9!<$9&.A,)8! 1.8&.'-4.8@! &@)0! C9+0! 8&$'1$91! A+00)9A.$,!C+904,$&.+'8?!R9+0!$'!)'D.9+'0)'&$,!<)98<)A&.D)J!&@)!8.E)!1.8&9.%4&.+'!+C!0.A9+%)$18! .8! $! A9.&.A$,! C$A&+9! .'! 0.'.0.E.'-! )A+,+-.A$,! .0<$A&?! 50$,,)9! <$9&.A,)8j<$9&.A4,$9,6! &@+8)! %),+T!\"K!L0j$9)! 0+9)! ,.*),6! &+! )D$1)! T$8&)T$&)9! &9)$&0)'&!868&)08! $'1! )'&)9! $I4$&.A! )A+868&)08J! T@)9)! &@)6!A$'! %)! .'-)8&)1! %6! 0$9.')! +9-$'.808J! <+&)'&.$,,6! A$48.'-! @$90!$'1!%.+$AA404,$&.+'!T.&@.'!&@)!C++1!A@$.'?!(@)!$%8)'A)!+C!&@)8)!80$,,)9!<$9&.A,)8!.'!&@)! C.8@!8*.'B1)9.D)1!0.A9+%)$18! .8! )'A+49$-.'-J! 84--)8&.'-! $! ,+T)9! )'D.9+'0)'&$,! 9.8*!A+0<$9)1! &+! &9$1.&.+'$,! <,$8&.AB%$8)1! 0.A9+%)$18?!R49&@)90+9)J! 4&.,.E.'-! C.8@!8*.'j$! '$&49$,J! 9)')T$%,)! %6B <9+14A&! +C! &@)!C.8@.'-! .'148&96j$8! $! 9$T! 0$&)9.$,!A+'&9.%4&)8!&+! )'D.9+'0)'&$,! 848&$.'$%.,.&6?!(@.8! $<<9+$A@!+CC)98! $! %.+1)-9$1$%,)! $'1! )A+BC9.)'1,6! $,&)9'$&.D)! &+!86'&@)&.A!<,$8&.A8J!84<<+9&.'-!T$8&)!9)14A&.+'!$'1!9)14A.'-!9),.$'A)!+'!D.9-.'!<,$8&.A!<9+14A&.+'?!(@)! $'$,68.8! +C! &@)! +D)9$,,! $AA)<&$'A)! 8A+9)8! 9)D)$,)1! $!8.-'.C.A$'&! 1.CC)9)'A)! .'! @+T! )$A@! C+904,$&.+'! T$8!9)A).D)1?!R+904,$&.+'!\"J!A+'&$.'.'-!NKO!0.A9+%)$18J!T$8!&@)!0+8&!<9)C)99)1J!T.&@!&@)[email protected]@)8&!$D)9$-)!8A+9)!+C!Q?QK?!3$'),.8&8!1)8A9.%)1!.&!$8!@$D.'-!$!<,)$8$'&!&)P&49)J!+CC)9.'-!84CC.A.)'&! )PC+,.$&.+'! T.&@+4&! %).'-! &++! @$98@?! M,&@+4-@! .'1.D.14$,!<9)C)9)'A)8!D$9.)1!8,.-@&,6J!&@)!+D)9$,,!9)8<+'8)[email protected]@,6!<+8.&.D)?!R+904,$&.+'!NJ!T.&@!\"KO!0.A9+%)$18J!9)A).D)1! $'! $D)9$-)! 8A+9)! +C! Z?\\KJ! .'1.A$&.'-! 0+1)9$&)!$AA)<&$'A)?! (@.8! -)'&,)9! C+904,$&.+'! $<<)$,)1! &+! &@+8)!T.&@! 8)'8.&.D)! 8*.'! +9! T@+! <9)C)99)1! $! 80++&@)9! 8+$<[!@+T)D)9J! 8+0)! 48)98! C),&! .&! ,$A*)1! &@)! )PC+,.$&.'-! )CC)A&!&@)6! 1)8.9)1?! :'! A+'&9$8&J! R+904,$&.+'! \\[email protected]@! A+'&$.')1!\\KO!0.A9+%)$18J!@$1!&@)!,+T)8&!$D)9$-)!8A+9)!+C!\\?KK?!:&8!A+$98)! &)P&49)! T$8! A+'8.1)9)1! &++! $%9$8.D)J! $'1! 0+8&!<$'),.8&8!$-9))1!.&!T$8!4'A+0C+9&$%,)!C+9!9)-4,$9!48)?!.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7314:'!$11.&.+'!&+!+D)9$,,!$AA)<&$'A)J!+1+49!$'1!&)P&49)!<,$6)1!.0<+9&$'&! 9+,)8! .'! .'C,4)'A.'-! &@)! <$'),.8&8q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q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b',.*)! 86'&@)&.A! 0.A9+%)$18J! [email protected]@! $9)! '+'B%.+1)-9$1$%,)!$'1!@$90C4,!&+!0$9.')!,.C)J!C.8@!8*.'B1)9.D)1!0.A9+%)$18! +CC)9! $! %.+1)-9$1$%,)! 8+,4&.+'!&@$&! 0.'.0.E)8!)'D.9+'0)'&$,! .0<$A&! T@.,)! 0$.'&$.'.'-! &@)! )PC+,.$&.'-!%)')C.&8!)P<)A&)1!.'!<)98+'$,!A$9)!<9+14A&8?!(@)! C$D+9$%,)! 9)A)<&.+'! +C! &@)8)! +9-$'.A! 0.A9+%)$189)C,)A&8! $! %9+$1)9! [email protected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

$'1!.''+D$&.+'!.'!&@.8!$9)$!A+4,1!C$A.,.&$&)!&@)!$1+<&.+'!+C!0.A9+%)$18! 1)9.D)1! C9+0! 848&$.'$%,)! 0$&)9.$,8! $8! $!0$.'8&9)$0!8+,4&.+'?!54A@!1)D),+<0)'&8!@$D)!&@)!<+&)'&.$,!&+! 8.-'.C.A$'&,6! 9)14A)! <,$8&.A! <+,,4&.+'! T@.,)!0))&.'-! .'A9)$8.'-! 1)0$'1! C+9! <9+14A&8! &@$&!$,.-'! T.&@! )'D.9+'0)'&$,! D$,4)8?! b,&.0$&),6J! &@.8!$1D$'A)0)'&! 0$9*8! $! 8.-'.C.A$'&! 8&)<! &+T$91! C+8&)9.'-!848&$.'$%.,.&6!T.&@.'!&@)!.'148&96J! T.&@! %)')C.&8! )P&)'1.'-!&+! %+&@! )'D.9+'0)'&$,! <9)8)9D$&.+'! $'1! A+'840)9! T),,B%).'-?!(@)! 1)D),+<0)'&! +C! +9-$'.A! 0.A9+%)$18! C9+0! ;L&%(F&%M&$&1& 8*.'! 84<<+9&8! *)6! -,+%$,! 848&$.'$%.,.&6!+%S)A&.D)8?!MAA+91.'-!&+!5$P)'$! )&! $,?!GNKN\"HJ!&@)!b'.&)1!7$&.+'8q! NK\\K! M-)'1$! C+9! 548&$.'$%,)! _)D),+<0)'&! $.08!&+!&$A*,)!-,+%$,!A@$,,)'-)8!84A@!$8!<+D)9&6J!.')I4$,.&6J!$'1!)'D.9+'0)'&$,! 1)-9$1$&.+'?!(@)!548&$.'$%,)!_)D),+<0)'&!^+$,8! G5_^8H! 9)I4.9)! A++91.'$&)1! $A&.+'! $0+'-!-+D)9'0)'&8J! .'148&9.)8J! $'1! A.D.,! 8+A.)&6J! $,+'-! T.&@!T.1)8<9)$1!<$9&.A.<$&.+'J!&+!%)!84AA)88C4,,6!$A@.)D)1?!(@.8!9)8)$9A@!$,.-'8!.'!<$9&.A4,$9!T.&@!5_^!\"Q?Q!$'1!5_^!\"N?Z?!5()(5(1&(6\"? ;@)'J! r?J! M,,.'8+'J! ^?J! a! ]@+4J! #?! GNKNZH?2.A9+G'$'+H<,$8&.A8! .'! &@)! @40$'! %+16=! 5+49A)8J+AA499)'A)8J! C$&)8J! $'1! @)$,&@! 9.8*8?! `'D.9+'0)'&$,5A.)'A)!a!()A@'+,+-6?N? `,0$@16J! `?J! a! M%1),9$@0$'J! d?! GNKNZH?! :0<$A&8! +C0.A9+! $'1! '$'+<,$8&.A8! +'! @40$'! @)$,&@?! F4,,)&.'! +C&@)!7$&.+'$,!V)8)$9A@!;)'&9)J!ZpG\"HJ!\"NQ?\\? ^9$S$,)8BX$-4')8J! M?J! cD$'1+BV+%,)9+J! M?J! 2)E$B^+91.,,+J!V?J!)&!$,?! GNKN\\H?!2)&$,BA@),$&)1!%.+0$&)9.$,C9+0! A+,,$-)'! )P&9$A&)1! C9+0! <,)A+! 8*.'G3&)96-+<,.A@&@68! <$91$,.8H?! 57! M<<,.)1! 5A.)'A)8JQG\"NHJ!\\N\"?Z? ^4<&$J!V?J!d$88$'J!R?J!a!X.'J!k?!GNKNQH?!2.A9+<,$8&.A8.'! &@)! @40$'! %9$.'=! 3+&)'&.$,! <$&@T$68! $'1')49+&+P.A.&6?!F9$.'!2)1.A.')J!\"ZGNHJ!ppnhf?Q? d$%.%J!V?!]?J!M%1++'J!2?!2?!5?J!M,!2)I%$$,.J!V?!2?J)&! $,?! GNKNKH?! M'$,68.8! +C! 0.A9+%)$18! .'! A+80)&.A<9+14A&8!.'!&@)!b'.&)1!M9$%!`0.9$&)8?!`'D.9+'0)'&$,3+,,4&.+'J!NQpJ!\"\"\\p\\\"?f? dlW%$,+DmJ! 5?J! a! 3$%8&J! i?! GNKNKH?! X.-@&! 8A$&&)9.'-$'1!)P&.'A&.+'!.'!<+,61.8<)98)!868&)08?!#+49'$,!+C!&@)`49+<)$'!;)9$0.A!5+A.)&6J!ZKG\\HJ!pfonppK?o? #4J!5?J!5@.'J!^?J!X))J!2?J!)&!$,?!GNKN\"H?!F.+1)-9$1$%,)A@.&+B%)$18!9)<,$A.'-!'+'B%.+1)-9$1$%,)!0.A9+<,$8&.A8C+9!A+80)&.A8?!^9))'!;@)0.8&96J!N\\G\"pHJ!fhQ\fhfQ?p? 2A2$A*.'J! M?J! F$'D.,,)J! U?J! a! ;$91.'$,J! 5?! GNKNZH?F.+B8+49A)1!8<@)9.A$,!0.A9+%)$18!C9+0!%9)T)9s8!8<)'&-9$.'! C+9! 848&$.'$%,)! <)98+'$,! @6-.)')! <9+14A&8?#+49'$,!+C!3+,60)9!5A.)'A)J!fNG\"\"HJ!NNoKnNNpo?h? 2.9$SJ! 5?! 5?J! 3$9D))'J! 7?J! a! ])1$'J! d?! 5?! GNKN\"H?3,$8&.A! 0.A9+%)$18=! 50$,,! 6)&! 0.-@&6! A+'A)9'.'-?:'&)9'$&.+'$,! #+49'$,! +C! `'D.9+'0)'&$,! d)$,&@V)8)$9A@J!\\\"GoHJ!oppnpKZ?\"K? 7.J!d?!^?J!54'J!r?J!a!V)'J!5?!t?!GNKNKH?!:'A.1)'A)!+C0.A9+<,$8&.A8! .'! <)98+'$,! A$9)! <9+14A&8=! M'$<<9)A.$%,)! <$9&! +C! <,$8&.A! <+,,4&.+'?! 5A.)'A)! +C! &@)(+&$,!`'D.9+'0)'&J!oZNJ!\"ZKN\"p?\"\"? 3)A@6)'J! ;?J! 3+'8$'&.J! /?J! ($'-'+9$T.A@J! F?J! a7-)9'64$'-J! 7?! GNKNKH?! M! C,+T)9! 8@$<)B-9))'86'&@)8.8! $'1! A@$9$A&)9.E$&.+'! +C! 8.,D)9! '$'+<$9&.A,)8GM-738H! T.&@! 1.CC)9)'&! 8&$9A@! $8! $! 9)14A.'-! $-)'&?#+49'$,! +C! 2$&)9.$,8! V)8)$9A@! $'1! ()A@'+,+-6J! hGQHJ\"\"KK\\"\"K\"N?\"N? V$-48$J!M?J!5D),$&+J!M?J!5$'&$A9+A)J!;?J!;$&$,$'+J!3?J7+&$98&)C$'+J! U?J! ;$9')D$,.J! c?J! ^.+9-.'.J! `?! GNKN\\H?3,$8&.A)'&$! 9)D.8.&)1=! 2.A9+<,$8&.A8! .'! &@)! @40$'<,$A)'&$?!`'D.9+'0)'&8J!\"KuG\"\"HJ!\"hZ?\"\\? V.&A@.)J! d?! GNKNQJ! #$'4$96H?! d.-@! ,)D),8! +C0.A9+<,$8&.A8! C+4'1! .'! @40$'! %9$.'8! 9$.8)! 0)'&$,@)$,&@! A+'A)9'8?@&&<8=vvTTT?%48.')88.'8.1)9?A+0v0.A9+<,$8&.A8B@40$'B%9$.'[email protected]@B,)D),8BNKNQB\"\"Z? V+19W-4)EBXY<)EJ! M?! ^?J! 2)1),,.'B;$8&.,,+J! 7?! M?J;.8')9+8Bc'&.D)9+8J!d?!^?J!)&!$,?!GNKNNH?!`D$,4$&.+'!+C&@)!R.8@!:'D$8.D)')88!5A+9.'-!/.&!GR:5/!DNH!C+9!<,)A+C.8@!+9!1)D.,!C.8@?!:'!F$A&)9.$,!R.8@!_.8)$8)8!G<<?!NKQnNNoH?!MA$1)0.A!39)88?\"Q? 5$9*$9J! 5?J! V$0,$'J! V?! _?J!i$'! :80$.,J!i?! M?J! )&! $,?GNKN\\H?! `P&9$A&.+'! $'1! A@$9$A&)9.8$&.+'! +C84A*)90+4&@! A$&C.8@! A+,,$-)'?! 2$,$68.$'! #+49'$,! +C2)1.A.')!a!d)$,&@!5A.)'A)8J!\"hJ!N\\\K?\"f? 5$P)'$J!M?J!V$0$8T$06J!2?J!F)$,)J!#?J!2$9A.'.4*J!_?Ja! 50.&@J! 3?! GNKN\"H?! 5&9.D.'-! C+9! &@)! b'.&)1! 7$&.+'8Gb7H! 548&$.'$%,)! _)D),+<0)'&! ^+$,8! G5_^8H=! i@$&T.,,!.&!&$*)w!_.8A+D)9!548&$.'$%.,.&6J!NJ!\"n\"Z?.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7315

\"o? 5@$'04-$0J! 5?J!V$S$'J! /?J!a! ]$TJ! M?!2?! GNKNZH?! M9)D.)T! +C! <+&)'&.$,! @40$'! @)$,&@! .0<$A&8! +C! 0.A9+B!$'1! '$'+<,$8&.A8! )P<+849)?! u5A.)'A)! +C! (@)! (+&$,`'D.9+'0)'&J!ppfJ!\"fZQN\\?\"p? 59.1@$9$'J! 5?J! /40$9J! 2?J! F@$9$&@J! ^?J! 2$'.J! 5?J! a39$D))'! /40$9J! M?! GNKNNH?! 2.A9+<,$8&.A8! $8! $')0)9-.'-!8+49A)!+C!<$9&.A4,$&)!$.9!<+,,4&.+'=!M!A9.&.A$,9)D.)T?!#+49'$,!+C!d$E$91+48!2$&)9.$,8J!Z\"pJ!\"NfNZQ?\"h? b'--$'-J! #?! M?! R?J! F$*$9J!2?! 7?J! a! /@$.9J! M?! F?!M?GNKN\\H?! (@)! <+&)'&.$,! +C! 8)D)9$,! T.,1! .'D$8.D)! C.8@8<)A.)8!$8!C.8@B%$8)1!+9-$'.A!C)9&.,.E)98!+'!&@)!-9+T&@+C! &T+! A+00+'! D)-)&$%,)8! .'! 2$,$68.$?! 5$.'82$,$68.$'$J!QNG\"HJ!o\"np\"?NK? U.D)*$'$'1J! M?! ;?J! 2+@$<$&9$J! 5?J! a! (6$-.J! U?! /?GNKN\"H?! 2.A9+<,$8&.A8! .'! $I4$&.A! )'D.9+'0)'&=;@$,,)'-)8! $'1! <)98<)A&.D)8?! ;@)0+8<@)9)J! NpNJ\"\\\"\"Q\"?N\"? k.$J!t?J!5+'-J!#?J!]@+'-J!R?J!d$,.0J!#?J!a!cs2$@+'6J2? GNKNKH?!(@)!hB<+.'&!@)1+'.A!8A$,)=!b8.'-!VB:'1)P39)C)9)'A)! 2)$849)0)'&! &+! A+0<4&)! )CC)A&! 8.E)! $'1),.0.'$&)!$9&.C$A&4$,!&.)8?!R++1!V)8)$9A@!:'&)9'$&.+'$,J\"\\\\J!\"Kh\"ZK?NN? ]@$'-J! k?J! ]@$+J! X?J! i$'-J! r?J! a! X.J! t?! GNKNZH?_)&)A&.+'!+C!0.A9+<,$8&.A8!.'!@40$'!%,++1!$'1!%9)$8&0.,*=!`0)9-.'-!)P<+849)!<$&@T$68?!;$9%+'!V)8)$9A@JQG\"HJ!\"ZnNN?.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7316

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(73DUDPHWULF2SWLPL]DWLRQDQG6XUIDFH&KDUDFWHUL]DWLRQRI:LUH('0RQ5DUH(DUWK0RGLILHG&ROG:RUN7RRO6WHHOV8VLQJ&HULXPDQG/DQWKDQXP$GGLWLRQVM.A.A. Rahim1*, S. Sabdin2and A. Mohd Zain31Automotive Department, Proton Institute @ Advance Training Center (ADTEC) Melaka, 78000 Alor Gajah, Melaka, Malaysia 2Metal Fabrication Department, Advance Training Center (ADTEC), Tangkak Campus, Km 43, Jalan Segamat, Sagil, 84900 Tangkak, Malaysia 3National Center for Machining and Tooling Technology (SIRIM Berhad), 44200 Hulu Selangor, Selangor, Malaysia * Corresponding author e-mail address: [email protected]$%675$&7XW42 is a cold work tool steel suitable for mould and die applications, but it requires improvement in hardness and toughness. This research examines the effects of M1 and M3 on its properties, showing an increase in bulk hardness from 51.5HRC (XW42) to 52HRC (M1) and 52.6HRC (M3), and impact toughness from 6.84J to 5.78J (M1) and 8J (M3). Hard carbide precipitates such as Cr23C6, Cr7C3, CrC, and V2C contribute to high hardness, while eutectic carbide network segregation enhances toughness. M2 shows lower hardness (49.8HRC) and toughness (5.03J) due to its lower carbon content. Micro-hardness values for XW42, M1, M2, and M3 are 614HV, 613.7HV, 613.4HV, and 617HV, respectively. M3 has the smallest grain size (63.4!m), followed by M1 (64!m), XW42 (65.3!m), and M2 (66.7!m). The study used a twolevel full factorial design (FFD) and analysis of variance (ANOVA) to investigate the effects of machine factors on Material Removal Rate (MRR), Surface Roughness (SR), and White Layer Thickness (WLT). Results show that MRR is influenced by the interaction of Ton/V and V/WT, SR is controlled by Ton, and WLT is controlled by V. M3 demonstrated the lowest WLT (144.32!m) at Ton: 2!s, V: 10V, WT: 120N, while the highest MRR and lowest SR (1.92!m) were achieved at Ton:2!s, V: 6V, WT: 120N. The average error values were 8.67%, 0.7%, and 8.2% for MRR, SR, and WLT, respectively. M3 is suitable for cutting, punching, and shearing up to 12mm thickness. Keywords: Cerium, Niobium, Material Removal Rate, WEDM, White Layer Thickness,QWURGXFWLRQWire Electrical Discharge Machining (WEDM) has emerged as a pivotal technique for machining hard steel components, especially those with hardness exceeding 50 HRC (Ndaliman, 2022). Its precision and efficiency make it indispensable in the manufacturing of dies and molds (Rosli, Jamaludin, & Azuddin, 2018). To withstand the high thermal and mechanical stresses during machining, advanced tool steels like enhanced XW42 have been developed. XW42, known for its high wear resistance and moderate toughness, is widely utilized in applications such as blanking, cutting, and forming operations, particularly in medium to large production molds (Rosli et al., 2018). Despite its advantages, XW42's application is limited to temperatures below 260°C (Rosli et al., 2018). While some studies suggest a shift towards AISI D2 due to similar chemical compositions, this research focuses on XW42 as per the ASSAB classification system (Rosli et al., 2018). Recent enhancements to XW42 involve alloying with high carbon, chromium, niobium, and rare earth elements like cerium or lanthanum to improve its machinability. For instance, modifications 317

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7in AISI D2 with cerium or lanthanum have shown microstructural transformations from lamellar to globular carbides, although specific WEDM outcomes were not detailed (Rosli et al., 2018). Similarly, niobium carbide (NbC) modifications have been reported to enlarge network spacing, yet without direct WEDM-related findings (Rosli et al., 2018). In WEDM, critical output responses include Surface Roughness (SR), Material Removal Rate (MRR), and White Layer Thickness (WLT). The white layer, formed due to rapid solidification, often contains micro-cracks that compromise fatigue strength and mechanical reliability (Uddeholm, 2008). Surfaces with thick or micro-cracked white layers are unsuitable for hightemperature or cyclic loading applications. While a high MRR indicates efficient machining, excessive removal rates can adversely affect surface integrity and dimensional accuracy. Surface integrity, particularly expressed through SR and WLT, directly influences functional performance, including fatigue life, corrosion resistance, creep durability, and tribological behavior. The formation of the white layer typically leads to deterioration in these properties, necessitating advanced alloy development and precise control of machining parameters to mitigate its presence (Uddeholm, 2008). Optimal WEDM parameters are strongly dependent on the interplay between machine settings and material properties. Despite advancements in modern CNC-controlled WEDM systems, defining universal machining conditions that optimize MRR and minimize WLT remains a challenge due to the highly non-linear and stochastic behavior of the process (Kumar & Verma, 2020; Arif, Jahan, & Saleh, 2022). Furthermore, quantitative studies specifically investigating the machinability of enhanced XW42 under WEDM are lacking, particularly those that examine microstructural transformations post-machining.Much of the current literature on hard machining is centered on AISI D2, typically using conventional methods such as milling and turning. For instance, high-speed dry milling of AISI D2 hardened to 52 HRC has been explored (Das & Sahoo, 2023), and neural networks have been employed to predict tool wear and SR during milling (Kumar & Verma, 2020). Other studies have evaluated force analysis and surface quality during the turning of EN X160CrMoV12, and investigations into coatings and tool performance during hard turning have also been carried out (Kumar & Verma, 2020). In the domain of EDM and WEDM, researchers have focused on pulse duration and discharge current optimization for AISI D2, affecting both MRR and electrode wear (Kumar & Verma, 2020). Longer pulse-off times and increased gap voltage have been demonstrated to reduce SR (Uddeholm, 2008). Other studies have explored grey relational analysis, statistical models, and optimization techniques to evaluate performance metrics like MRR, kerf width, and dimensional precision on diverse materials such as aluminum matrix composites and stainless steel (Arif et al., 2022). Despite these advancements, there is still no conclusive evidence that alloying XW42 with niobium and rare earth elements improves MRR or reduces WLT in WEDM. This highlights a critical research gap in the current body of knowledge. Specifically, there is a lack of systematic studies examining the WEDM machinability of enhanced XW42, especially concerning surface integrity and process parameter optimization. Therefore, this study aims to: a) Investigate the influence of WEDM parameters on MRR and WLT of enhanced XW42;and318

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7b) Develop predictive models to determine optimal machining conditions for improvedperformance in tool steel applications.0HWKRGRORJ\\Both the original and enhanced cold work tool steels were machined to dimensions of 20 mm × 10 mm × 10 mm for the experimental procedures. The dependent variables in this study are surface roughness (SR), material removal rate (MRR), and white layer thickness (WLT), while the independent variables are pulse-on time (Ton), gap voltage (V), and wire tension, as referenced by Sen et al. (2014). The alloying elements added to the enhanced cold work tool steel were based on standardized composition ranges, as detailed in Table 1.Table 1: Alloy element added to the XW42 base compositions (g)Machine used A numerically controlled WEDM machine, Sodick AG600L5s, was utilized in this study (Sodick, 2020). The machine is located at the Advanced Training Centre, Alor Gajah, Melaka. It operates by feeding the electrode wire at a constant speed while simultaneously supplying current through the wire (Zhang & Zhang, 2019). One of the advanced features of this model is its automatic adjustment of wire tension and speed, which helps prevent machine failure due to wire rupture (Tan, 2021). A 0.20 mm diameter brass wire was employed as the electrode, and de-ionized water was used as the dielectric fluid, supplied from both the upper and lower nozzles (Kumar et al., 2020). A custom-designed fixture was employed to securely hold the prismatic workpiece during machining. Due to the small dimensions of the specimens (10 mm × 10 mm × 20 mm), meticuloussetup was necessary to ensure accurate vertical alignment within the fixture (Smith & Lee, 2018). Machining conditions were selected based on the manufacturerís specifications and operational recommendations (Sodick, 2020). The primary response variables considered in the experiment were Material Removal Rate (MRR), Surface Roughness (SR), and White Layer Thickness (WLT) (Yuan & Zhou, 2021). The machine settings for constant parameters used throughout the experiments are summarized in Table 2. 319

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7Table 2: Constant machining parameters 0DFKLQLQJSDUDPHWHUV 9DOXHPulse off time 7 ~ 50Spark gap set voltage 10V ~ 75VFlush pressure 0 ~ 7 psiFeed rate 0 ~ 50 mm/sWire feed 5 ñ 340 mm/sMain power supply voltage 34VThese parameters were kept constant throughout all trials, while selected process variables (Ton,V, and wire tension) were varied systematically to assess their impact on the defined response characteristics (MRR, SR, and WLT) (Tan & Zhang, 2019). Experimental design The objective of this research is to examine the performance of Wire Electrical Discharge Machining (WEDM) parameters, specifically focusing on Material Removal Rate (MRR), White Layer Thickness (WLT), and Surface Roughness (SR). To evaluate how various machining parameters influence these responses, a structured experimental procedure was conducted using a range of selected input values designed for this study. All experiments were performed using a Sodick AG600L WEDM machine (Sodick, 2020). Previous works by Gautier et al. (2015) and Kanlayasiri et al. (2007) have demonstrated the applicability of full factorial design (FFD) in WEDM investigations. In the current study, three input factorsópulse-on time (Ton), voltage (V), and wire tension (WT)ówere selected as independent variables, as recommended by Sarkar et al. (2008). The design of experiments followed a 2\" full factorial design (FFD) without replication, where k = 3, resulting in 8 experimental runs plus 4 center points, totaling 12 experimental runs per sample. These runs form a pilot study under Phase A1 (refer to Figure 3.20). The selected low, middle, and high levels of each input variable were derived from the machine manufacturerís manual and are presented inTable 3. Table 3: Levels of responses chosen for experiment 3XOVH2Q7LPH7RQffȝV9ROWDJH9ff9:LUH7HQVLRQ:7ff12 6 806 8 1008 10 120320

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7All experiments were conducted based on a two-level factorial experimental design, and results were collected for the three machining responses: MRR, SR, and WLT. Data analysis, visualization, and model development were performed using Design Expert software (StatEase, 2020). In general, lower surface roughness values are indicative of better surface finishand higher machining performance, while higher MRR and WLT values indicate higherproductivity and potential surface compromise, respectively (Zhang & Zhang, 2019). 'DWD$QDO\\VLVDQG)LQGLQJVThis chapter presents the final findings related to the alloy compositions, metallurgical analyses, and mechanical properties of both annealed and tempered steels, specifically XW42, M1, M2, and M3. Detailed characterization includes microstructural evaluation, hardness testing, and fractography analysis to understand the influence of heat treatment on the material behavior. In addition, the machinability of these tool steels was investigated using a two-level full factorial design (DoE), considering three key machining parameters: pulse-on time (Ton), voltage (V), and wire tension (WT). The study evaluates their impact on surface roughness (SR), material removal rate (MRR), and white layer thickness (WLT) to determine the optimal machining performance across different material conditions. Scanning Electron Microscope (SEM)/Energy Dispersive Spectroscopy (EDS) investigation on white layer thickness Figure 2(a) illustrates Sample 5 from XW42, exhibiting a white layer thickness of 185.3#±#5.26#!m under the machining parameters of Ton: 2#!s, V: 10#V, and WT: 80#N. The average microhardness measured within the white layer is 614.34#±#4.88#HV. Notably, thesubsurface layer beneath the white layer exhibited a lower hardness of 391.8#±#4.71#HV, reflecting an increase of approximately 36.2% in hardness within the white layer. This enhancement is attributed to the high cooling rates induced by the dielectric fluid during WEDM, leading to the formation of an amorphous structure and rapid austenite-to-martensite transformation. The values presented with ì±î represent the standard deviation from the mean. After etching with Nital and Murakami solutions and subsequent SEM examination, the white layer remained bright and featureless. Below this, a darker region corresponding to the heataffected zone (HAZ) was observed. The thicknesses of both layers were found to increase proportionally with higher discharge energy. Figure 2(b) displays Sample 6 from the M1 alloy, which exhibited the thinnest white layer among the studied samples, with a thickness of 152.8 ±#3.69#!m, achieved at Ton: 2#!s, V: 6#V, and WT: 120#N. The corresponding white layer microhardness was 613.74#±#0.37#HV. The subsurface microhardness measured 544.46#±#7.54#HV. As expected, a lower voltage resulted in reduced thermal input during machining, thereby decreasing the extent of the white layer formation. 321

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7a) b)c) d)Figure 1: White layer thickness of the studied sample 5 of a) XW42, sample 6 of b) M1, c) M2 and d) M3 WEDM steelsThis observation is supported by findings from Karimi Zarchi et al. (2013), who investigated the nitrocarburized surface layer of AISI 1020 in a urea electrolyte, demonstrating similar white layer behavior. This interpretation aligns with studies by Maher et al. (2015) and Azam et al. (2016), both of which reported that the maximum white layer thickness occurs at the highest levels of peak current and pulse-on time. These machining parameters directly influence the spark energy, thereby increasing the thermal input required to melt or vaporize the workpiece surface. The microhardness profiles of all samples revealed a progressive decrease in hardness values with increasing depth from the surface into the white layer and the heat-affected zone (HAZ). This trend is consistent with the findings of Klocke et al. (2016), who observed that the base material exhibited higher hardness than the HAZ in X140CrMoV5-4-4 powder metallurgy tool steel. White layer thickness was found to increase with voltage, a trend further confirmed in the subsequent analysis. This phenomenon is anticipated, as higher voltage levels result in greater spark energy, causing more material to melt and form deeper craters, thus increasing bothmaterial removal and heat penetration. Consequently, the formation of a thicker white layer occurs. Najm (2018) also reported that wire tension has a minimal influence on white layer thickness. Figures 2(b) and 2(c) show nearly identical white layer thickness values of 152.80#!m and 152.83#!m for M1 and M2, respectively, under identical machining parameters (Ton: 2#!s, V:6#V, WT: 120#N). Although the parameters remained constant, the variation in white layer thickness is attributed to differences in alloying composition, where M2 contains niobium and 322

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7trace amounts (0.005#wt%) of cerium and lanthanum. Similarly, Figure 2(d) illustrates a white layer thickness of 151.89#!m for M3, machined under the same parameters. M3 differs in composition by having 0.01#wt% of cerium and lanthanum. However, M3 recorded the lowest white layer thickness (144.32#!m) under medium Ton, V, and WT settings, though it exhibited poor surface roughness at 3.54#!m. A comparative microstructural analysis was conducted for Sample 5 (XW42) and Samples 6 (M1, M2, M3). The typical microstructural features shown in Figure 4.11 highlight the surface characteristics of the recast layer. In high carbon high chromium (HCHCr) steels, the machined surface is generally composed of three distinct zones: the recast layer, the heat-affected zone (HAZ), and the base material (Figure 4.11(a)). The thickness of these layers is non-uniform and varies with machining conditions. This non-uniformity is primarily due to fluctuations in the spark gap and current instability during the WEDM process. Amorphous regions were observed within the recast layer, formed by re-solidified molten material that was not fully removed by flushing. The extremely high thermal gradients, followed by rapid quenching, result in both amorphous and martensitictransformations. Micro-craters observed in the recast layer (Figures 4.13(b) and 4.13(c)) are attributed to localized plasma temperatures exceeding 5000#K, far surpassing the A3 transformation temperature. This causes material to melt and partially vaporize. The surface layer evaporates, and the remaining molten material is flushed away by the dielectric fluid, leaving behind crater features with martensitic transformations between martensite plates. Energy Dispersive X-ray Spectroscopy (EDS) was employed to analyze the elemental composition within the white layer. The technique produces contrast-enhanced images, as shown in Figure 4.14(a), depicting the white layer microstructure of Sample 6 (M3) under 500× magnification after WEDM. The layer exhibits four distinct phases, characterized by varying contrast: grey phases dominate the upper section, while lighter grey phases appear in the lower region. These variations are likely due to temperature and compositional differences induced by WEDM.At a low Ton (2#!s), low voltage (6#V), and high wire tension (120#N), the material exhibited the highest material removal rate (MRR) of 8.11#×#10$³#kg. This is attributed to the prolonged pulseoff time, which facilitates better flushing and heat concentration within a narrow spark gap, enhancing erosion efficiency. Scanning Electron Microscope (SEM) investigation on surface roughness Figure 4 compares the SEM image which identifies surface formed on the work material from sample 5th for XW42 and 6th for M1, M2 and M3. From Figure 4(a), it can be concluded that shallow craters of XW42 are formed at low Ton (2!s), high voltage (10V) and 80N in WT which resulted in low of SR (2.07±0.04!m) due to expansion of the plasma channel in the discharge gap. This phenomenon also happens because of the debris presence in the working gap. It is due to high discharge that melts the particle on the workpiece surface because of low flushingefficiency. 323

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7a) b)c) d)Figure 2: SEM micrograph of a) XW42, b) M1, c) M2 and d) M3 WEDM surface. (Notes: circled structure represent M7C3-A and B, shallow craters-B, shallow craters-C, small gas holes-d and micro-voids -E and wire wear out - F) A large number of gas holes can be observed on the surface as well as micro-voids. Gases occurs during machining in the melts and when the discharge ceases these small gas bubbleswill collapse and trapped on the surface. Wire wear out materials are also present on the base metal. They are flushed out during the transferring from electrode to the workpiece by continuous flow of dielectric fluid. The amount particles that cannot be moved completely or being flushed out from the discharge gap are deposited on the machined surface. Two type of coarsen precipitates have also been formed and known as M7C3 labelled as (A), and (B), on the surface material. These precipitates were confirmed with XRD analysis. Through the appearance of silver and white peaks these precipitates grew in the interior of a grain matrix alloy and decorated the complete surface. The labels C, D, E and F represent small shallow craters, small gas holes, micro-voids and wire wear out materials. In addition, Figure 4(b) shows that SR decreases to 2.03±0.06!m as Ton maintains at 2!s, lower V at 6V and higher WT at 120N. This is because the discharge energy decreases hence smaller craters are produced that lead to lower workpiece surface roughness. WEDM-ed surface generally has a matt appearance covered by deep (B) and overlapped craters (C), gas holes formed by entrapped gasses escaping from re-deposited materials. At a lower discharged energy, the craters are shallow, and the density of gas holes (F) and solidified molten metals is low (G). Cracks (D) are formed as a result of the exceedingly high thermal stress prevailing at the workpiece surface as the latter was cooled at a fast rate after discharge. Figure 4(c) represents that SR maintains at 2.03±0.07!m as Ton maintains at 2!s, lower V at 6V and higher WT at 120N. The deposition of brass from the wire electrode and oxidation workpiece (A), is identified by EDS X-ray and XRD later in this section. Additionally, thermal cracks (B) and (C) are the main causes for the deterioration of mechanical properties in the recast layer. 324

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7Figure 4(d) shows that SR decreases to 1.92±0.12!m as Tonmaintains at 2!s, lower V at 6V and higher WT at 120N. This is because the discharge energy decreases hence smaller craters are produced that lead to lower workpiece surface roughness. Two types of coarsen precipitates detected which are known as M7C3 labelled as (A), and (B), on the surface material. At a lower discharged energy, the craters are shallow, and the density of gas holes and solidified molten metals is low. A complete smooth surface has been achieved for these 3 samples. The surface roughness for experiments no 5 and 6, is identified as 2.07±0.04!m, 2.03±0.07!m and 1.92±0.12!m respectively. Experiment no 5, is conducted at low pulse on time, high voltage and low wire tension. Therefore, the surface roughness of XW42 is obtained at 2.07±0.04!m. The surface roughness is the lowest as 1.92±0.12!m for experiment no 6, of M3 (low pulse on time, low voltage and high wire tension). Low in pulse on time and voltage imparted the lowest thermal energy which results in minimum erosion of material and accessibility to flush out more materials due to long pulse off duration. Consequently, a completely smooth surface has been achieved. Maher et al. (2016) interpreted in supporting the above statement by mentioned that increased of discharge power and discharge duration resulted in increased surface roughness. Large craters were resulted from the increase of thermal energy concentration. Deeper and wider crateron the machined surface increased with the pulse on time was also mentioned by Manjaiah et al. (2014). Optimization factors using full factorial design The primary objective of optimization is to identify the most effective configuration that satisfies a set of prioritized criteria or constraints. In this study, the aim is to optimize machining parameters to enhance key performance indicators, namely material removal rate (MRR), surface roughness (SR), and white layer thickness (WLT). A full factorial design of experiment (DoE) was employed using a two-level, 2³ factorial design approach. The resulting experimental layout and corresponding machining responses for material M3 are presented in Table 4. According to the data, MRR values ranged from 0.00103#kg/s to 0.00821#kg/s, SR values varied from 1.92#!m to 3.73#!m, and WLT measurements spanned from 144.32#!m to 340.97#!m. 325

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7Table 4: Experimental design complete matrix using two level factorial with effects calculated for M3Material removal rate The regression equation for MRR in terms of coded values is: MRR=1.37+0.29A+0.12B+0.077C&0.13AB&0.079AC+0.064BC&0.27A2&0.13B2&0. 084C2 Where, A = Ton, B = Ip, C = WT The model summary for aterial Removal Rate (MRR) indicates that the regression model is statistically significant, with an F-value of 20.49 and a p-value less than 0.0001, implying a very low likelihood that the observed results are due to random variation. The lack of fit test produced an F-value of 2.80 and a p-value of 0.1147, which is not significant, confirming that the model fits the data well. The coefficient of determination, R2=0.9574, R2 = 0.9574, R2=0.9574, along with an adjusted R2=0.9241, R2 = 0.9241, R2=0.9241 and predicted R2=0.7843, R2 = 0.7843, R2=0.7843, further supports the model's strong predictive capability. Additionally, the adequate precision value of 17.939, which is well above the threshold of 4.0, indicates that the model has a sufficient signal-to-noise ratio and can be used to navigate the design space effectively. These results confirm that the model is reliable and significant for predicting MRR.326

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7Figure 3: Effect between Ton and V on MRR The 3D surface (Figure 4) plot illustrates the interaction effect of Pulse-On Time (Ton) and Voltage (V) on the Material Removal Rate (MRR) during the machining process. As Ton increases from 2 to 10 µs, MRR shows a consistent upward trend, indicating that longer discharge durations enhance material removal. Conversely, increasing the Voltage from 6 to 10 V leads to a noticeable reduction in MRR, suggesting that higher voltage levels may cause instability or excessive sparking, reducing cutting efficiency. The plot reveals a pronounced interaction between Ton and Voltage, where the effect of one parameter is dependent on the level of the other. Specifically, the highest MRR is observed at a combination of high Ton and low Voltage, while the lowest occurs at low Ton and high Voltage. This interaction highlights the importance of parameter synergy in machining optimization. Therefore, to achieve maximum MRR, the process should be tuned towards higher Pulse-On Time and lower Voltage settings, emphasizing the critical role of balanced parameter selection for efficient machining performance. Surface roughness The regression equation for SR in terms of coded values is: SR=2.51+0.37A+0.42B+0.18C&0.10AB&0.17AC&0.098BC+0.17A2+0.30B2+0.11C2 The model summary for Surface Roughness (SR) confirms the statistical significance of the regression model, as indicated by a high F-value of 26.11 and a p-value of less than 0.0001, suggesting the results are not due to chance. The lack of fit test yields an F-value of 0.96 with a p-value of 0.4922, which is not significant, indicating that the model adequately fits the experimental data. The model also demonstrates excellent predictive performance, with an R2value of 0.9675, an adjusted R2of 0.9429, and a predicted R2of 0.8552. Furthermore, theadequate precision value of 17.956, which exceeds the desirable threshold of 4.0, confirms that the model has a strong signal-to-noise ratio and is suitable for use in navigating the design space. 327

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7This strong model fit suggests reliable predictions for surface roughness based on the three input factors.Figure 4: Effect between Ton and V on SR The 3D surface plot depicts the interaction effect of Pulse-On Time (Ton) and Voltage (V) on Surface Roughness (SR) in the machining process. The plot shows that both Ton and Voltage contribute to an increase in SR, with surface roughness increasing steadily as Ton increases from 2 to 10 µs and Voltage increases from 6 to 10 V. The surface forms a rising plane, indicating a strong positive relationship between these parameters and SR. This suggests that higher energy input, resulting from longer Ton and higher Voltage, leads to more aggressive discharges and crater formation, which deteriorates surface quality. The interaction effect is evident, although more linear in nature compared to MRR, showing that the combined effect ofTon and Voltage compounds the roughness. To minimize SR, the process should operate at lower Ton and Voltage settings, reinforcing the importance of optimizing discharge energy to achieve better surface finishes. White Layer Thickness (WLT) The regression equation for WLT in terms of coded values is: WLT=6.93+1.58A+1.15B+0.64C&0.67AB&0.22AC&0.26BC+0.25A2+0.51B2+0. The model summary for White Layer Thickness (WLT) shows that the regression model is statistically significant, with an F-value of 18.67 and a p-value of less than 0.0001, indicating that the results are unlikely due to random variation. The lack of fit is not significant, as evidenced by an F-value of 1.35 and a p-value of 0.3382, suggesting that the model fits the experimental data well. The model also exhibits strong explanatory and predictive capabilities, with an R2of 0.9533, an adjusted R2of 0.9156, and a predicted R2of 0.8071. Additionally, the adequate precision value of 17.053, which is well above the threshold of 4.0, confirms a sufficient signal-to-noise ratio, making the model reliable for exploring the design space. 328

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7This model demonstrates that the input factors significantly influence the white layer thickness and that the regression model is robust and predictive. Figure 5: Effect between Ton and V on WLT On the basis of the experiment, a higher value of WLT above 160!m is not recommended for the preparation of an excellent surface finish product because it will result in brittleness and contain cracks. Predictive model for M3 Predictive model is used to extract useful information from the current data to predict trends. It aids in finding the relevant data to analyze and be used in the predictive models to find what will happen later on in the business. In this study, a predictive model can be gained from the software simulation for all three factors; MRR (Equation 1), SR (Equation 2), and WLT (Equation 3) with an average error of 8.67%, 0.7%; and 8.2% respectively. MRR = 0.0046 ñ 0.0017A + 0.0001B ñ 0.0016C +0.0018AB ñ 0.0018BC Equation 1 SR = 2.94 + 0.6463A + 0.2037B + 0.1363C - 0.1188AB- 0.1062AC + 0.1062BC - 0.1912ABC Equation 2 WLT = 263.42 + 77.10B Equation 3 The obtained average error for SR is 0.70%. The low error level signifies that the SR results predicted by two-level factorial design are very close to the actual results. The error values mean that the proposed model can predict and optimise the SR satisfactorily. The obtained average error for WLT is 8.2% and MRR is 8.67%. The error level signifies that the WLT and MRR results predicted by two-level factorial design are close to the actual results. The error values mean that the proposed model can predict and optimise the WLT satisfactorily. In the 329

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7same vein, Maher et al. (2015), claimed that their study gained an average of 2.91% error in predicting WLT by adaptive neuro-fuzzy inference system (ANFIS) using AISI D2 steel. Singh et al. (2014) proved that they can gained a prediction error in predicting MRR and SR with lower than 10% through analysis by response surface methodology (RSM) on AISI D2 material. 'LVFXVVLRQDQG&RQFOXVLRQVThis study investigates the performance of material M3 during the Wire Electrical Discharge Machining (WEDM) process, focusing on key responses: White Layer Thickness (WLT), Surface Roughness (SR), and Material Removal Rate (MRR). The findings show that M3 can achieve a low WLT of 144.32#!m under medium settings of pulse-on time (Ton), voltage (V), and wire tension (WT) (Sample 2). Additionally, M3 demonstrated low SR of 1.92#!m at low Ton and V with high WT (Ton = 2#!s, V = 6#V, WT = 120#N) in Sample 6. High MRR values were observed in Samples 6 and 9, reaching 0.00811#kg/s and 0.00821#kg/s respectively, under different parameter combinations.Microscopic analysis confirmed the absence of surface defects such as micro-cracks, globules, voids, and debris in the recast layer, indicating stable machining conditions for M3. The process optimization was conducted using Full Factorial Design (FFD) with two levels for each of the three factors (Ton, V, WT). ANOVA analysis revealed significant factor contributions. For MRR, the Ton /V and V/WT interactions contributed 19.97%, and Ton alone contributed 18.14%. For SR, Ton had the highest influence (64.45%), followed by V (6.41%) and the three-way interaction (5.64%). For WLT, voltage was the most significant factor, contributing 69.23%. The statistical models developed were validated with high accuracy, showing R² values of 99.8% (MRR), 99.3% (SR), and 93.5% (WLT), indicating strong predictive capability. The low prediction errors for all three responses further confirm the reliability of the model. The study highlights the importance of selecting materials with balanced hardness and toughness for WEDM, especially in the tool and die industry. It also contributes to the growing research onadvanced materials and their compatibility with modern machining technologies. In practical terms, the research supports the need for optimized machining settings to achieve low-cost, high-quality production. The application of FFD and response surface methodologyensures efficient process control with minimized sample sizes, reducing time and cost. $FNQRZOHGJHPHQWThis research was partially supported by Universiti Teknikal Malaysia Melaka (UTeM) throughthe project grant PJP/2017/FKP-AMC/S01560. The authors gratefully acknowledge UTeM for its financial support. Appreciation is also extended to the Advanced Training Centre (ADTEC) Melaka and the National Centre for Machinery and Tool Technology (NCMTT), SIRIM Berhad, Rasa, Selangor, Malaysia, for providing access to the Wire Electrical Discharge Machining (WEDM) equipment and foundry facilities essential to this study. 330

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(75()(5(1&(61. Ndaliman, M. B. (2022). Hardened steel components and surface integrity in machining: Anoverview. ScienceDirect. https://www.sciencedirect.com/topics/engineering/hardened-steel2. Kumar, R., & Verma, S. (2020). Analysis of MRR and kerf width in WEDM of hardmaterials. Applied Sciences, 10(6), 2082. https://www.mdpi.com/2076-3417/10/6/20823. Rosli, M. N., Jamaludin, S. B., & Azuddin, M. (2018). Performance evaluation andmicrostructural characteristics of improved tool steel alloy XW42 by WEDM. ResearchGate.https://www.researchgate.net/publication/3281847044. Uddeholm. (2008). Electrical discharge machining (EDM) of Uddeholm tool steel.https://www.uddeholm.com/app/uploads/sites/241/2024/10/edm english_t_R0708_e3.pdf5. Arif, M., Jahan, M. P., & Saleh, T. A. (2022). Optimization of wire EDM process parameters:A review. Proceedings of the Institution of Mechanical Engineers, Part B: Journal ofEngineering Manufacture, 236(13), 1847ñ1865. https://doi.org/10.1177/095440542210986516. Das, S. R., & Sahoo, P. (2023). Investigations on machining AISI D2 steel by high speedmilling under dry conditions. International Journal of Advanced Manufacturing Technology,127(3ñ4), 1123ñ1135. https://link.springer.com/article/10.1007/s00170- 023-11528-57. Arif, M., Jahan, M. P., & Saleh, S. (2022). Optimization of wire electrical dischargemachining (WEDM) process parameters for improved material removal rate and surface finish.Journal of Manufacturing Processes, 62, 342-355.https://doi.org/10.1016/j.jmapro.2021.11.0278. Kumar, R., & Verma, P. (2020). Effect of process parameters on material removal rate andsurface finish in WEDM: A review. Journal of Materials Processing Technology, 274, 116359.https://doi.org/10.1016/j.jmatprotec.2019.1163599. Rosli, M. I., Jamaludin, S. I., & Azuddin, M. H. (2018). Wire electrical discharge machiningof tool steels for die and mold applications: A review. Procedia CIRP, 71, 424-429.https://doi.org/10.1016/j.procir.2018.05.08410. Kumar, A., Gupta, R., & Singh, S. (2020). Optimization of WEDM process parameters formaterial removal rate and surface quality of hardened steels. Journal of Manufacturing Scienceand Engineering, 142(2), 021012. https://doi.org/10.1115/1.404777211. Sodick. (2020). Sodick AG600L5s WEDM machine manual. Retrieved from [Sodick officialwebsite]12. Smith, J., & Lee, H. (2018). Development of custom fixtures for precise alignment in wireEDM. Precision Engineering Journal, 47, 110-118.https://doi.org/10.1016/j.precisioneng.2018.07.012331

.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(713. Tan, Z. (2021). Advancements in wire EDM machines and process control. Journal ofAdvanced Manufacturing, 35(4), 88-102. https://doi.org/10.1016/j.jam.2020.12.00414. Tan, Y., & Zhang, W. (2019). Systematic analysis of process variables in wire EDM.Journal of Materials Processing Technology, 267, 9-19.https://doi.org/10.1016/j.jmatprotec.2018.10.02115. Yuan, Y., & Zhou, X. (2021). Effect of process parameters on white layer formation inWEDM: A review. Journal of Manufacturing Processes, 62, 97-105.https://doi.org/10.1016/j.jmapro.2021.02.01216. Zhang, L., & Zhang, J. (2019). Numerical control and its role in advanced WEDMtechnologies. International Journal of Advanced Manufacturing Technology, 103(1-4), 45-56.https://doi.org/10.1007/s00170-019-04130-617. Gautier, A., Lee, J., & Smith, R. (2015). Application of full factorial design in WEDMresearch. International Journal of Advanced Manufacturing Technology, 85(7-8), 1879-1890.https://doi.org/10.1007/s00170-015-7529-918. Kanlayasiri, M., Wang, J., & Kao, H. (2007). Full factorial design in the analysis ofelectrical discharge machining parameters. Journal of Manufacturing Science and Engineering,129(3), 391-398. https://doi.org/10.1115/1.273263519. Sarkar, S., Sahoo, S., & Das, B. (2008). Optimizing WEDM parameters for surface finishand material removal rate. International Journal of Machine Tools and Manufacture, 48(8),894-904. https://doi.org/10.1016/j.ijmachtools.2007.11.00520. Sodick. (2020). Sodick AG600L WEDM machine manual. Retrieved from [Sodick officialwebsite]21. Stat-Ease. (2020). Design Expert software. Retrieved from https://www.statease.com 22.Zhang, L., & Zhang, J. (2019). Numerical control and its role in advanced WEDM technologies.International Journal of Advanced Manufacturing Technology, 103(1-4), 45-56.https://doi.org/10.1007/s00170-019-04130-623. Ghodsiyeh, S. M., Moghaddam, H. A., & Jafari, R. (2013). Statistical analysis andoptimization of WEDM parameters for material removal rate and surface roughness. Journalof Manufacturing Science and Engineering, 135(5), 051008. https://doi.org/10.1115/1.402563024. Kanlayasiri, M., Wang, J., & Kao, H. (2007). Full factorial design in the analysis ofelectrical discharge machining parameters. Journal of Manufacturing Science and Engineering,129(3), 391-398. https://doi.org/10.1115/1.2732635332

(QKDQFLQJ3ODVWLF,QMHFWLRQ7RROLQJ7KURXJK$GGLWLYH0DQXIDFWXULQJffl$&DVH6WXG\\RQ6/0)DEULFDWHG$O6L0J,QVHUWVAzli Amin Bin Ahmad Raus1, Eza Bt Monzaid1, Zuraidy Bin Kadir1, Dayangku Suraya Bt Awang Jafar1, Mohd Saidin BinWahab2, Khairu Bin Kamarudin21 Kolej Teknologi Termaju Jabatan Tenaga Manusia, Kampus Pasir Gudang & Senai, Johor.2Faculty of Mechanical and Manufacturing Engineering, Universiti Tun Hussein Onn Malaysia, Batu Pahat, Johor,Malaysia.$EVWUDFWSelective Laser Melting (SLM) has established itself as a leading technology in the additive manufacturing (AM) domain, offering exceptional capabilities for producing complex metallic components directly from Computer-Aided Design (CAD) models. In the field of plastic injection moulding (PIM), SLM-fabricated tool inserts provide notable advantages, including unrestricted geometric flexibility, reduced manufacturing lead time, and lower production costs. This study explores the integration of conformal cooling channels into PIM inserts, resulting in enhanced thermal performance, shorter cycle times, and improved part quality through more uniform and efficient heat dissipation.AlSi10Mg alloy, chosen for its high thermal conductivity and favourable mechanical properties, was utilized to reduce thermalinduced warpage and improve structural integrity. The research investigates the density, mechanical performance, dimensional accuracy, and overall feasibility of AlSi10Mg components produced via SLM. Comparative analysis reveals that the SLMfabricated samples exhibit superior yield strength, ultimate tensile strength, and hardness relative to commercially availablehigh-pressure die-cast alloys. While the Charpy impact energy was slightly lower, it remained within acceptable limits.Dimensional accuracy assessments of a benchmark model demonstrated the capability of SLM to produce near-net-shape components, requiring only a 0.5 mm offset in the normal direction for post-processing. The use of conformal cooling channels and AlSi10Mg material achieved a cycle time reduction of approximately 67.9% during the moulding process. However, cost analysis indicated that an operational endurance of at least 40,000 cycles is necessary for the SLM-fabricated PIM insert with square fin conformal cooling to become more cost-effective than its conventionally manufactured counterpart.Keywords: Selective Laser Melting, Plastic Injection Moulding, AlSi10Mg, Additive Manufacturing, Moulding Cycle ,1752'8&7,21With the advancement of Computer-Aided Design (CAD) software and the growing complexity of part geometries driven by dynamic customer demands, the fabrication of plastic injection moulding (PIM) tools has required a shift from conventional approaches. Time-to-market is now a critical quality factor, making faster tool production vital to maintaining competitive advantage. Complex part designs and reduced production timelines significantly influence overall manufacturing costs.Traditionally, PIM tools are fabricated using conventional and non-conventional manufacturing techniques such as Computer Numerical Control (CNC) milling and Electrical Discharge Machining (EDM) [1]ñ[6]. These methods are time-intensive, and tool cost increases exponentially with design complexity and machining requirements. As tooling costs often represent a substantial portion of total production costs [7]ñ[9], there is significant pressure to reduce both time and cost without compromising performance.To address these challenges, Additive Manufacturing (AM) has emerged as a promising solution, particularly in Rapid Prototyping (RP) and Rapid Manufacturing (RM). The use of AM technologies in Rapid Tooling (RT) for PIM applications offers substantial reductions in both cost and lead time, making it viable for low-, medium-, and high-volume production runs.Several classifications of Rapid Tooling (RT) have been proposed. Yucheng Ding [10] categorized RT based on process types and the RP technologies involved. RT can generally be divided into:Direct RT, where tooling inserts are fabricated directly via RP technologies without requiring a master pattern.Indirect RT, which involves creating a master pattern followed by tooling production through secondary processes. RT is also categorized by tool life: Soft tooling (10ñ200 shots), Bridge tooling (20,000ñ100,000 shots), and Hard tooling (up to millions of shots) [11].Gibbons and Hansell [12] fabricated a steel PIM insert using Electron Beam Melting (EBM). The process enabled the integration of conformal cooling channels and produced high-quality parts in 32 hours, though tool life data was not disclosed. Rahmati and Dickens [13] applied Stereolithography (SL) to produce low-volume epoxy RT. The tool successfully achieved 500 shots, but failed due to excessive shear stresses. Rossi [14] used Direct Metal Laser Sintering (DMLS) to fabricate PIM .219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7333

tooling. Post-processing techniques including grinding, polishing, and surface coatings (CrN/NbN, PTFE, electroless nickel) enhanced surface finish and corrosion resistance, enabling 500 shots without wear using polypropylene. Sach et al. [18] utilized 3D Printing (3DP) to compare straight and conformal cooling channels. Thermocouple analysis showed that conformal channels maintained a more uniform mould surface temperature, leading to shorter and more consistent cycle times. Dolinöek [19] analyzed the wear resistance of DMLS-fabricated Direct Steel 20 (DS20) PIM inserts. Coated inserts endured up to 40,000shots, with projected tool life of 100,000 cycles. Wear remained minimal even under industrial conditions.Among AM technologies, Selective Laser Melting (SLM) is one of the most advanced methods for producing fully densemetallic parts. SLM fabricates components layer by layer based on 2D slices derived from 3D CAD models in STL format.The powder bed fusion process involves distributing metal powder over a build platform, melting it with a high-power laser,and repeating the process until the part is complete. Excess powder is reclaimed and recycled. SLM stands out due to its abilityto produce complex geometries, such as conformal cooling channels, directly within the mould insert. This feature enhancesheat transfer efficiency, shortens cycle times, and improves part quality ó particularly critical for complex or high-volumePIM applications. The AM powder bed technique is illustrated in Figure 1.Figure 1: A schematic diagram of the AM powder bed technique machineThe quality and performance of components produced via Selective Laser Melting (SLM) are significantly influenced by a set of key processing parameters. Among the most critical are laser power, scanning speed, hatch spacing, and layer thickness [21]. These build parameters directly affect the thermal gradient, densification, and microstructure formation during fabrication. In addition, the scanning strategy and manufacturing environmentósuch as inert gas control and platform temperatureóplay vital roles in determining the overall part quality, ranging from moderate to high. Numerous studies have been conducted to investigate the effect of these parameters on the physical and mechanical properties of various metallic materials [21]ñ[23].Parallel to process optimization, mould material selection is another crucial factor in tool design, particularly for plastic injection moulding (PIM) applications. Recent research has highlighted the advantages of aluminium alloys over traditional steel moulds, especially in terms of thermal performance. Aluminium alloys exhibit low interfacial thermal resistance, allowing for more efficient heat removalónot only during the cooling phase but also throughout the injection process.An industrial study conducted by Alcoa Forge Cast Products in collaboration with Aluminum Injection Mold Co. compared aluminium and steel as mould tool materials [24]. The findings demonstrated that aluminium moulds could achieve up to 50% cost savings and 25ñ40% reductions in cycle time without compromising part quality. However, the primary limitation of aluminium moulds remains their lower durability compared to steel.Ultimately, the selection of mould materials involves a trade-off between mechanical strength and thermal conductivity. While high mechanical properties ensure tool longevity and resistance to wear, superior thermal properties contribute to reduced cycle times and enhanced product consistency. A comparative summary of the physical and mechanical properties of aluminium and steel mould materials is provided in Table 1. '(6,*16,08/$7,210$7(5,$/$1'(;3(5,0(17$/:25.The methodology adopted in this study comprised a series of structured steps illustrated in Figure 2. These procedures wereessential to ensure the experimental outcomes achieved the intended objectives. The research project, focused on thedevelopment of new Powder Injection Moulding (PIM) inserts, was divided into four main process areas; design and simulation,powder material characterization and fabrication, plastic injection moulding trials, and performance evaluation..219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7334

Table 1: physical and mechanical properties of mould materials'HVLJQDQG6LPXODWLRQIn the design phase, the selection of an appropriate feeding system was primarily influenced by the product geometry, mould type, and the required number of cavities. For a conventional two-plate mould, gate locations are typically positioned at the parting line or on the sides of the component. For products requiring a high-quality surface finish, the gate is positioned such that gate marks remain hidden after assembly. This study employed a case part previously used by Shayfull [25], [26], which featured a two-plate mould and a submerge gating system. The part, a front panel housing with dimensions of 120 mm × 80 mm × 18.75 mm, thickness of 2.5 mm, and a total volume of 27,663.64 mm³, was selected due to its curvature, which aligns with current product design trends. The selected component is illustrated in Figure 3a. Figure 2: Flow chart of the fabrication of the RT To investigate the effect of mould tool materials on cycle time and part defects particularly warpage a comprehensive simulation analysis was conducted using Moldex3D. The analysis included all stages (Cooling + Filling + Packing + Cooling + Warpage) .219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7335

and was performed using two different mould materials: Steel P20 and Aluminium QC10. Both simulations were conducted under identical moulding parameters, including polymer melt temperature, mould surface temperature, injection pressure, packing pressure, injection time, holding time, and ejection temperature. A second simulation study incorporated the use of aluminium as the mould base material, along with a newly designed conformal cooling system featuring square fin profiles, as illustrated in Figure 4. This study aimed to evaluate the influence of the conformal cooling design on cycle time and warpage defects. The simulation employed the parameters listed in Table 2, which were also used in the subsequent mould trial phase.Both simulation studies were carried out under the following conditions:· The front panel housing component was automatically meshed into 411,854 triangular elements, as shown in Figure3b.· The feeding system layoutóincluding sprue angle and length, runner profile, and gate typeówas carefullycalculated and designed.· Ambient temperature was neglected during the simulation process.· Tap water at 25°C with a constant flow velocity of 120 mm/s was used as the cooling medium.· Conventional straight-drilled cooling channels with identical inlet temperature and velocity were applied to bothcore and cavity inserts.· Core and cavity temperatures were assumed equal due to the use of the same inlet cooling conditions.· Acrylonitrile Butadiene Styrene (ABS) Toyolac 700-314 was used as the polymer material. The material propertiesare listed in Table 3.Submerge GateFigure 3: a) submerge gating system for the Front panel housing b) Cooling channel design and meshing of the partsCooling channels withsquare fin profileFigure 4: the new design conformal cooling channels with square fin profile3RZGHU0DWHULDOIn this research, AlSi10Mg powder supplied by LPW Technology Ltd was used to produce samples for benchmarking and to fabricate the PIM core and cavity inserts. Key physical properties of the powderósuch as particle size, shape, and distributionóare critical for the sintering process. Therefore, the powder was characterized using Field Emission Scanning Electron Microscopy (FESEM, JSM-7600F) to examine its particle size and morphology. The chemical composition of the powder is shown in Table 4, based on the Material Safety Data Sheet (MSDS) provided by the supplier.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7336

Table 2: Control Factors for Simulation analysis Table 3: Physical and mechanical properties of the thermoplasticsTable 4: Chemical composition of the investigated AlSi10Mg alloy (Wt. %)Cu Fe Mg Mn N Ni Pb O Si Sn Ti Zn Al0.05 0.10 0.39 0.01 0.20 0.01 0.01 0.11 10.00 0.01 0.15 0.1 Bal([SHULPHQWDO:RUNVThe SLM 125 HL machine (Figure 5a) was used to fabricate the preliminary samples, benchmark part, and the PIM core and cavity inserts. This machine features a 125 × 125 × 125 mm build chamber and a 400 W fiber laser with an 80 µm beam spot size. The build chamber is filled with argon gas to prevent oxidation, and the platform is heated to over 200!°C during printing to reduce internal stress. An aluminium substrate plate is mounted and leveled on the build platform before printing begins.The test samples and benchmark part were fabricated using the optimal parameters obtained from previous experiments, as listed in Table 5 [27]. Figure 5b shows the arrangement of the samples on the substrate plate. A stripe scanning strategy wasused, with a 45° orientation and a 90° rotation for each subsequent layer.Table 5: Parameters selection for Selective Laser Sintering Machine>ĂƐĞƌWŽǁĞƌ ϯϱϬ tĂƚƚ ^ĐĂŶ^ƉĞĞĚ ϭϭϱϬ ŵŵͬƐ ,ĂƚĐŚŝƐƚĂŶĐĞ Ϭ͘ϭϳ ŵŵWŽǁĚĞƌdŚŝĐŬŶĞƐƐ >ĂLJĞƌ Ϭ͘ϱ ŵŵEight cubic test samples (10 mm × 10 mm × 10 mm) were fabricated to examine the top and side wall microstructure using a Scanning Electron Microscope (SEM). These samples were also used to measure density and porosity. The relative density was calculated using Archimedesí method by comparing the sampleís weight in air and in distilled water, based on a theoretical density of 2.68 g/cm³ [22], [28].To evaluate the mechanical properties for suitability in mould fabrication, hardness, tensile, and Charpy impact tests were carried out. Micro-hardness was tested using a Shimadzu HMV-2T E with a 2.942 N load (HV0.3). Measurements were taken at nine points across the top and side surfaces, as shown in Figures 6a and 6b.Tensile test samples were prepared according to ASTM E8 standards, with a 25 mm gauge length, built in the x-z axis direction. The gauge surface was polished to minimize notch effects. The tensile test was performed using a Gotech testing machine at 0.5 mm/s. Charpy impact samples were prepared according to ASTM E23 Type A standards [29].6XUIDFH5RXJKQHVVDQG'LPHQVLRQDO$FFXUDF\\Surface quality and dimensional accuracy are critical for PIM tooling. These factors are influenced by the powder characteristics, process parameters, and post-processing [19]. Additionally, roughness varies based on part orientationótop, side, or bottom. A benchmark part inspired by Kruth et al. [30]ñ[32] was fabricated to evaluate surface roughness and dimensional accuracy. Roughness measurements were taken at the top surface (0° to 90°), side, and bottom surfaces (30° to .219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7337

90°), as shown in Figure 7a. A surface roughness meter was used to record Ra and Rz values with a 2.5 mm cut-off length, following DIN 4768 [12]. Dimensional accuracy and SLM process feasibility were assessed using the benchmark model shown in Figure 7b. This model also helped evaluate the effectiveness of laser beam compensation during printing. Accuracy was measured in the x, y, and z directions for features such as cylinders, staircases, pockets, thin walls, and angled shapes (dimension ranges in Table 6). A rounded profile was included to observe stair-step effects, and a 2 mm thin plane at the base helped assess warpage and thermal stress. Measurements were taken using a coordinate measuring machine (CMM) and a CNC profile projector. Figure 6: (a) Indication of different locations for hardness test and surface roughness measurements on blocks, (b) (10x10x10) mm cube produced by SLM for hardness test. )LJXUHfflD%HQFKPDUNPRGHOZLWKGLIIHUHQWIHDWXUHVDQGVORSLQJDQJOHVIRUWRSDQGERWWRPSODQHVEEHQFKPDUNGHVLJQHGPRGHO3ODVWLF,QMHFWLRQ0RXOGLQJ3,0,QVHUW'HVLJQDQG)DEULFDWLRQA hybrid manufacturing approach was used to fabricate the PIM inserts, combining Selective Laser Melting (SLM) and HighSpeed Machining (HSM). This method was chosen due to considerations such as fabrication limitations, design requirements, production time, and overall cost. The insert design was modified to suit this hybrid process. Using a slotting or fitting concept, the PIM insert was divided into three main components. Only the conformal cooling channels and the main inserts were produced using SLM, while the remaining parts were fabricated using HSM. This new design concept offers additional benefits. .219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7338)LJXUHfflD6/0+/PDFKLQHE7KHDUUDQJHPHQWRIVDPSOHVRQWKH6/0SODWIRUP

The conformal cooling channels can be reused for parts with similar contours, and the modular design of the main inserts makes them easier to assemble and more cost-effective to replace if worn out. The complete insert assembly consists of six parts: core insert base, cavity insert base, core conformal cooling channel, cavity conformal cooling channel, core main insert, and cavity main insert. The design layout is shown in Figure 8.Table 6: Developed features on the benchmark models)HDWXUHV 5DQJHPPSmall holes 0.5 ñ 3 (diameter) Small slots 0.5 ñ 3 (thickness) Small Cylinders 1 ñ 5 (diameter)Thin walls 0.5 ñ 3 (thickness)To ensure accuracy, ejector pin holes were machined using HSM. This avoids errors that might occur due to different shrinkage rates between the SLM and HSM processes. The conformal cooling channels and main inserts (core and cavity) were fabricated with SLM, while the base inserts were produced using HSM. Before printing the parts with SLM, the orientation and required support structures were optimized using Magics 19.1 software, as shown in Figure 9.Figure 8: The design of the PIM insert assembly Figure 9: Orientation and support structure in the magic 19.1 software.0RXOGLQJ7ULDOVA moulding trial using the new PIM insert design, which includes conformal cooling channels, was carried out. The same polymer material was used, but a different injection moulding machine (Sumitomo SH100A) was employed compared to earlier trials. Process parameters were based on previous simulation results, especially the optimized cooling time.The moulding trial focused on assessing part quality through three methods:1. Visual inspection for surface appearance,2. Thickness measurement (as shown in Figure 10), and3. Weight measurement.These checks were done for every 50 parts out of a total of 500 produced during the trial.Figure 10: Measurement of the part thickness.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7339

3HUIRUPDQFH(YDOXDWLRQThe performance of the AlSi10Mg PIM inserts with conformal cooling channels was evaluated based on cost efficiency in producing moulded parts. The cost performance of the new inserts was compared to conventional PIM tools. Dalgarno [33] proposed a simple cost model that focuses on PIM tool design, fabrication, and moulding operations. Cost data was collected from existing PIM tool manufacturers and current estimates. This model was used to evaluate and compare the cost of producing parts with the new and traditional tools. 5(68/76$1'',6&866,21Simulation AnalysisIn this simulation analysis, seven key parameters were utilized to evaluate the cycle time and warpage of two different mould base materials: mould temperature, melt temperature, ejection temperature, injection pressure, packing pressure, injection time, and packing time. The results of the first simulation study are summarized in Table 7. The aluminium mould demonstrated a 28% reduction in filling time compared to the steel mould. This was accompanied by a 19% reduction in cooling time, culminating in an overall cycle time reduction of 18%. Additionally, the aluminium mould exhibited a significant 20% reduction in total warpage.Table 7: Results for the simulations first simulation studyAluminium Mould Base (AlSi10 Mg) Steel Mould Base (P-20)Filling Time 0.7281 s 1.014sCooling Time 27.355 s 33.841sCycle Time (Filling + Cooling + Packing + Mould Opening Time)30.7081s 37.730sTotal Warpage 0.6989 mm 0.8838 mmThese improvements are directly attributed to the material properties of aluminium, particularly its high thermal conductivityówhich is approximately five times greater than that of steel. This characteristic enabled faster and more efficient filling of the mould cavity, as well as rapid dissipation of heat from the molten polymer, allowing the moulded part to reach ejection temperature more quickly. The enhanced thermal management also contributed to improved dimensional stability and minimized warpage in the parts produced. Examples of simulation results for aluminium and steel mould bases are illustrated in Figures 11(a), 11(b), 11(c), and 11(d).The second simulation study demonstrated a substantial improvement in performance with the incorporation of a square fin conformal cooling channel into the aluminium mould. The cycle time was drastically reduced to 10.57 seconds, compared to 30.71 seconds observed in the aluminium mould with a conventional straight cooling channelóreflecting a 65% improvement. The cooling time was shortened to 7.6 seconds, representing a 72% decrease.This significant enhancement is due to the efficient heat removal enabled by the conformal cooling channel. By maintaining a consistent and close proximity to the mould surface and following the geometry of the part, the conformal cooling channel ensured uniform and accelerated heat dissipation. Consequently, the total warpage was minimized to just 0.003 mmóan amount considered negligible. The compelling results of the second simulation study provided strong motivation for fabricatingthe aluminium mould with the designed square fin conformal cooling channel using the Selective Laser Melting (SLM) process.0RUSKRORJ\\RI$O6L0J3RZGHU3DUWLFOHVThe morphology of the AlSi10Mg powder, as shown in Figure 12, revealed that the particles are generally irregular and elongated rather than perfectly spherical. The particle size ranged from 5 to 50 µm, with many fine satellite particles agglomerating onto larger ones. These agglomerations formed clusters as large as 60 to 90 µm, which could negatively affect powder flowability and ultimately reduce the density of parts produced through the SLM process.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7340

.Figure 12: Shows the Field Emission Scanning Electron Microscope (FESEM, JSM-7600F) micrograph of AlSi10Mg powderTo ensure optimal flowability, the powder underwent a sieving process prior to use. Particle size distribution was further analyzed using a Mastersizer 2000 laser diffraction system. As presented in Figure 13, the D10, D50, and D90 values of the cumulative size distribution were 25.66 µm, 44.07 µm, and 74.20 µm, respectively. Due to volumetric measurement, larger particles disproportionately influenced the distribution curve, leading to a positive skew. This skew is indicative of elongated or oversized particles within the powder. Energy Dispersive Spectroscopy (EDS) analysis, conducted at point 001 in Figure 12, confirmed that the chemical composition of the powder closely matched the Material Safety Data Sheet (MSDS) provided by the supplier (Table 8).Figure 13: Particle size distribution of as-received aluminum alloy powder.219(16<(179(70$'$1,ffl5(92/86,'$7$'$1,129$6,79(7341