Investigation of Structural, Optical and Mechanical Properties of Poly (methyl methacrylate) / Zirconium oxide (PMMA/ZrO2 ) Nanocomposite Films

Investigation of Structural, Optical and Mechanical Properties of Poly (methyl methacrylate) / Zirconium oxide (PMMA/ZrO2 ) Nanocomposite Films | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Investigation of Structural, Optical and Mechanical Properties of Poly (methyl methacrylate) / Zirconium oxide (PMMA/ZrO2 ) Nanocomposite Films N. C. Horti, S. I. Mathapati, N. R. Banapurmath, V. S. Pujari, and 2 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4115396/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 28 Mar, 2025 Read the published version in Polymer Bulletin → Version 1 posted 7 You are reading this latest preprint version Abstract This research article explain the fabrication of poly (methyl methacrylate)/ zirconium oxide (PMMA/ZrO 2 ) nanocomposite films via a solution casting technique. The fabricated nanocomposite films were examined for their structural, morphological and optical properties through X-ray diffraction, Atomic force microscopy, Fourier infrared transform, UV-Vis absorption and fluorescence emission spectroscopy techniques. Thermogravimetric test was performed to check the thermal stability of nanocomposite films and the mechanical properties was assessed using a universal testing machine. XRD patterns of samples showed the formation of pure PMMA films and the successful incorporation of ZrO 2 nano-fillers into polymer matrix and the results are in good agreement with the FTIR results. The agglomeration of particles and change in surface roughness of films was noticed from AFM images. UV-Vis absorption analysis revealed that the absorption onset of PMMA films shifted towards a longer wavelength with an increasing content of ZrO 2 nano-fillers. The photoluminescence spectra exhibited the significant enhancement of photoluminescence intensity and a red shift in the emission peak of PMMA films as the content of ZrO 2 nanofillers increases. With an increase of ZrO 2 nanofiller concentration, the mechanical properties of composite films change significantly. The sample with 3% nano-filler exhibited the good mechanical strength, including a break energy of 4665 MJ/m 3 and a break stress of 3.390 MPa and superior photoluminescence intensity making it suitable composite material for denture-based applications. PMMA ZrO2 Nanocomposite Films Solution casting Optical and mechanical properties Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Introduction The design and fabrication of polymer/metal oxide nanocomposite films have gained considerable interest in recent years, owing to their novel optical, electrical, magnetic, and mechanical properties, as well as their widespread applications in the scientific, industrial, and medical fields [ 1 , 2 ]. The consistent distribution of nanofillers across the matrix, their enlarged interfacial area, and their interfacial interaction with the matrix materials can change these properties of the polymer nanocomposite films [ 3 ]. The homogeneous dispersion of nanofillers in the polymer matrix enhances loading efficiency and lowers local stress [ 4 ]. Furthermore, the particle size, shape, and concentration of nanofillers influence the properties of matrix material [ 5 ]. The concentration of nanofillers can have a significant impact on the various properties of nanocomposite films, including optical and mechanical properties. At higher nanofiller concentrations, the agglomeration/aggregation of nanofillers in the polymer matrix alters mechanical properties like low hardness, tensile modulus, and yield strength [ 6 ]. The addition of nanofillers generates new energy states in the matrix band gap, leading to an intriguing optical properties [ 7 ]. Polymers, namely polyaniline (PANI), polyvinylchloride (PVC), polythiophene (PTh), polycarbazole (PCz) and poly(methyl methacrylate) (PMMA) are being studied extensively for a wide range of applications including fuel cells, rechargeable batteries, corrosion resistance, optoelectronic devices, drug delivery, and medical applications [ 8 – 11 ]. PMMA is more popular than other organic polymers due to its superior properties such as, good electrical insulators, good chemical resistance, high optical transparency, good weather ability and thermal stability [ 12 , 13 ]. It also has exceptional mechanical properties such as dimensional stability, impact resistance, flexural strength, and fracture toughness, making it better material for denture-based applications [ 14 , 15 ]. In denture based application, the optical and mechanical properties play an important role. The addition of nanofillers such as metal, metal oxide, and carbon nanomaterials to polymer matrices can alter the opto-mechanical properties [ 16 ]. The series of metal oxides like SnO 2 , TiO 2 , MnO 2 and ZrO 2 have been used as filler materials in the polymer matrices due to their superior opto-mechanical properties [ 17 , 18 ]. Among the numerous metal oxides, ZrO 2 is an unique choice due to its outstanding properties such as good ionic conductivity, high optical transparency, high facture toughness, good mechanical strength and wideband gap of > 5 eV[ 19 , 20 ]. Because of these properties, ZrO 2 is a suitable filler material for the PMMA matrix to improve its optical and mechanical properties. Therefore, the fabrication of PMMA/ZrO 2 nanocomposite films using different fabrication techniques such as sol-gel[ 21 ], spin coating[ 22 ], spray pyrolysis[ 23 ],magnetron sputtering[ 24 ], solution casting[ 25 ] were reported. Solution casting technique has several advantages over the other methods mentioned above, including its simplicity, low cost, and low operating temperature. Until now, numerous studies on the optical and mechanical properties of PMMA films with different types of nanofillers have been reported. They indicate the distinctive optical properties due to the formation of new states within the band gap of matrix material, as well as the enhancement/reduction of mechanical strength [ 26 , 27 ]. Sengwa and Dhatarwal[ 28 ] used a solution casting technique with tetrahydrofuran as a solvent media to fabricate PMMA nanocomposite films with various nano-fillers (ZnO, SnO 2 and TiO 2 ). Because of the formation of certain localized states in the PMMA forbidden energy gap caused by the generation of structural defects, they exhibited a shift in the absorption edge towards a longer wavelength and a decrease in the value of the energy band gap as the concentration of nano-filler increased. Tekin et al [ 29 ] utilized a simple spin coating technique to fabricate PMMA/ZrO 2 and PMMA/WOxZrO 2 nano-comoposite films. They have observed the decrease in band gap of nanocomposite films as concentration of ZrO 2 nanoparticles increased due to increased carrier-carrier interaction, band levels approach of one another. By dissolving methyl methacrylate in chloroform and benzyl peroxide as a catalyst, a new spin casting technique was used to fabricate ZnO/PMMA nanocomposite films reported by Singh et al. [ 30 ]. The presence of intrinsic vacancies, such as Zn ions and oxygen vacancies, has been observed to produce blue-green emission peaks at 434 and 500 nm. The photoluminescence peak of ZnO/PMMA nanocomposite films has not significantly shifted due to the near band edge emission caused by band edge transitions or exciton recombination. Bay et al. [ 31 ] have reported the fabrication of PMMA/silica nanocomposite films by spin coting technique and examined the effects of free surfaces and internal interfaces on the mechanical properties of PMMA/silica nanocomposite films. As the thickness of the films increased, they observed a decrease in the stress value of PMMA films. However, there was no discernible change in the elastic modulus of the films when the concentration of nanoparticles loading increased. Martínez et al [ 32 ] reported the mechanical and optical properties of PMMA-GPTMS-ZrO 2 hybrid thin films were fabricated through a sol-gel route. They elaborated the improvement in hardness of the PMMA-GPTMS-ZrO 2 hybrid films with ZrO 2 content due to the strong chemical bond between PMMA and ZrO 2 nanoparticles. The synthesis of PMMA-ZnO nanocomposites with different weight percent of ZnO nanoparticles (2–5%) is reported by Ahmad et al [ 33 ]. In their investigation, they observed the enhancement in absorption intensity of PMMA-ZnO nanocomposites with weight percent of ZnO nanoparticles and the better antifungal efficacy against various candida species, indicating that this material could be a smart choice for denture application. Very recently, Kumari et al [ 34 ] developed the denture based PMMA and PMMA-ZrO 2 nanocomposites with different ZrO 2 content (2% -10%) using heat cure technique. They observed reduction of band gap as ZrO 2 content increases with the enhancement of mechanical properties for 5 wt % of ZrO 2 in PMMA including the maximum compressive strength (76.6 MPa) and fracture toughness (6.58 MPa-m 1/2 ). Based on these results, they came to the conclusion that the 5 wt % of ZrO 2 nanoparticles loaded PMMA/ZrO 2 nanocomposite is the better material for denture applications. A few studies on optical properties of PMMA/ZrO 2 nanocomposite films have been reported in literature, however the variation in mechanical properties of PMMA/ZrO 2 nanocomposite films with different concentration of ZrO 2 nanofillers have not been thoroughly investigated. The novelty of the present work involves PMMA a thermoplastic polymer that exhibits low mechanical strength and brittle on impact. Furthermore, the reinforcement of ZrO 2 nanofillers in PMMA matrix improves the mechanical rigidity and strength of the pure PMMA, rendering it a better alternative material for denture based applications. Therefore, in this work, we have fabricated PMMA/ZrO 2 nanocomposite films using a solution casting method. The effect of varying concentrations of ZrO 2 nanofiller on the structural, optical and mechanical properties of PMMA/ZrO 2 nanocomposite films is investigated. Materials and method Zirconium sulphate (SRL chemicals), sodium hydroxide (SD fine), poly(methyl methacrylate) (Himedia Lab.Pvt.Ltd), chloroform (Molychem) of analytical grade are used without any refinement. Fabrication of (PMMA/ZrO 2 ) Nanocomposite Films ZrO 2 nanoparticles with a particle size of 10.78 nm were synthesized through a chemical co-precipitation method, as provided in reference [ 35 ]. Using a magnetic stirrer, 1 gram of poly (methyl methacrylate) (PMMA) was dissolved in 100 ml of chloroform during a standard fabrication procedure. 3%, 5%, and 10% (see Table 1 ) of ZrO 2 nanoparticles were dispersed in 50 ml of chloroform. The obtained solution of ZrO 2 was mixed into the above PMMA solution drop wise, and the stirring was continued for 18 hours to complete the dispersion of ZrO 2 nanoparticles in the solution. Thereafter, the mixture was transferred into petri dish and allowed to slowly evaporate the solvent at room temperature for about 72 hours. Thereafter, a thin layer of nanocomposite was obtained. Finally, the solvent content and organic residues are removed from the obtained films by heating them for an hour at 60 o C in a hot air oven. Here, we indicated the pure PMMA film as P 0 and the PMMA film with 3%, 5% and 10% of ZrO 2 nanofiller as P 1 , P 2 , and P 3 respectively. Table 1 Stoichiometric values for the fabrication of nanocomposite films. Sample Name Weight of PMMA (gm) Weight of ZrO 2 Nanofiller (gm) P 0 1.0000 0.0000 P 1 0.9671 0.0309 P 2 0.9474 0.0526 P 3 0.8889 0.1111 Characterization details X-ray diffraction pattern of nanocomposite films were recorded by Rigaku, Ultima-IV, X-ray diffractometer. To understand the formation and vibration of various functional groups of the fabricated nanocomposite films, an FTIR spectrophotometer (Nicolet-6900) was utilized. A thermogravimertic analyzer (DST Q600) was used to verify the thermal stability of nanocomposite films. UV-Vis absorption spectrophotometer (JASCO, V-670) and fluorescence emission spectrophotometer (HORIBA, Fluromax-4) were used to measure the optical properties of the nanocomposite films. A universal testing machine (UTM, 10ST) was used to examine the tensile and compressive strengths of the fabricated films. Result and discussion X-ray diffraction study Figure 1 depicts the XRD pattern of samples P 0, P 1 , P 2 and P 3 . The XRD pattern of sample P 0 reveals the broad intense peak at 15.23 o is indexed to the (111) plane, while the less intense peak at an angle of 2θ = 29.83 o and 42.39 o are corresponds to the (112) and (211) planes, respectively [ 36 ]. These three peaks in the XRD pattern show the formation of pure PMMA, and the broadness of diffraction peaks suggests the amorphous nature of PMMA [ 37 , 38 ]. The XRD pattern of P 1 and P 2 samples show the diffraction peaks of PMMA (shown by an asterisk) along with extra peaks at 2θ = 30.15 o and 50.79 o respectively, which could be indexed to the (101) and (112) crystal planes of the tetragonal ZrO 2 phase. From XRD pattern of P 3 sample, we have noticed the XRD peaks of PMMA along with peaks at 30.15 o , 35.07 o , 50.79 o , and 60.69 o respectively, corresponds to the (101) (110) (112) and (211) planes of the tetragonal ZrO 2 phase and is in according to the JCPDS data: 81-1455 [ 39 ]. The sample P 3 exhibits a reduction in the height of XRD peaks associated with PMMA, indicating a stronger interaction between the ZrO 2 nanofillers and PMMA matrix at higher ZrO 2 nano-filler content. This indicates that ZrO 2 nanofiller is successfully incorporated into the PMMA matrix and the formation of PMMA/ZrO 2 nanocomposite films. Atomic Force Microscopy The surface topography of the fabricated films were analysed using Atomic Force Microscopy (AFM). The AFM instrument was operated in dynamic mode with vibration frequency of 150.487 kHz. Figure 2 shows the 3-D and 2-D AFM images of P 0, P 1 , P 2 and P 3 samples. The AFM image of sample P 0 shows the peaks of different heights with small irregularities indicates the grains are oriented randomly. Whereas, the change in surface irregularities for the samples P 1 , P 2 and P 3 is due to the agglomeration of ZrO 2 nanofillers. This change in agglomeration rate with concentration of ZrO 2 nanofillers is caused by the lower interfacial energy and the variation of interfacial interaction of oxygen atom of ZrO 2 nanofillers and methoxycarbonyl (C(O)OCH 3 ) group of PMMA chain. The average surface roughness (S avr ) and root mean square of surface roughness (S rms ) of fabricated nanocomposite films was estimated by following formulae [ 40 ]. $${S}_{avr}= \frac{1}{MN}\sum _{k=0}^{M-1}\sum _{i=0}^{n-1}\left|z({x}_{k}-{y}_{i})\right|$$ 1 and $${S}_{rms}= \sqrt{\frac{1}{MN}\sum _{k=0}^{M-1}\sum _{i=0}^{n-1}{\left[z({x}_{k}-{y}_{i}\right]}^{2}}$$ 2 The estimated values of average surface roughness and root mean square of surface roughness of fabricated nanocomposite films are listed in Table 2 . It is observed that as the concentration of ZrO 2 nanofiller increases, the values of S avr and S rms of nanocomposite films decreases due to the agglomeration of nanofillers. An increase of nanofiller concentration results in a decrease of interface energy and a stronger interaction. This accelerates the agglomeration rate of nanocomposite films, facilitating the growth of continuous layers and possibly reducing the surface roughness of nanocomposite films [ 41 ]. Table 2 Estimated values for the roughness of nanocomposite films. Sample Name S a (µm) S rms (µm) P 0 0.326 0.570 P 1 0.135 0.367 P 2 0.083 0.288 P 3 0.020 0.141 Fourier Transform Infrared spectroscopy The FTIR spectra of samples P 0, P 1 , P 2 and P 3 are displayed in Fig. 3 . In the FTIR spectrum of P 0 samples, the band at 481 cm − 1 appears due to the C–C in plane bonding and the band at 665 cm − 1 is due to the stretching vibration of the C-C = O group [ 42 , 43 ]. The band noticed at 758 cm − 1 is attributed to the C – C skeletal mode and the sharp band at 841 cm − 1 correspond to the CH 2 rocking vibration [ 44 , 45 ]. The bands centred at 989 cm − 1 and 1386 cm − 1 are assigned to the C-O-C stretching vibration and the deformation of O-CH 3 groups [ 45 – 47 ]. The band noticed at 1455 cm − 1 is ascribed to the asymmetric bending vibration of methyl (-CH 3 ) group [ 48 ]. The sharp band that appeared around at 1731 cm − 1 is because of the symmetric carbonyl (C = O) stretching of ester group, which confirms the formation of PMMA [ 49 , 50 ]. The band found at 2843 cm − 1 is related to the symmetric stretching vibration of CH group [ 51 ]. The strong bands identified at 2943 cm − 1 and 2996 cm − 1 are associated with the antisymmetric vibration of CH 3 and CH 2 groups [ 52 ]. The bands at 3439 cm − 1 , 3552 cm − 1 and 3623 cm − 1 are ascribed to the stretching vibration of C-H group [ 53 ]. FTIR spectrum of sample P 0 is consistent with other reports [ 54 , 55 ]. From FTIR spectrum of samples P 1 , P 2 and P 3 , we noticed the peaks of PMMA with a small hump around at 553 cm − 1 (indicated by circle) and is ascribed to the stretching vibration of Zr-O groups of ZrO 2 nanofiller [ 56 ]. The small shift of bands at 726 cm − 1 , 827 cm − 1 and 1487 cm − 1 correspond to the CH and CH 3 stretching vibration, indicates the good interaction of oxygen atom of ZrO 2 nanofiller with PMMA matrix via methoxycarbonyl (C(O)OCH 3 )group [ 57 ]. FTIR results confirm the better interaction of ZrO 2 nanofiller with PMMA matrix and the successful incorporation of ZrO 2 nanofiller into PMMA matrix. Thermogravimetric analysis Figure 4 depicts the result of thermogravimetric analysis (TGA) which is used to assess the thermal stability of fabricated nanocomposite films. The evaporation of solvents and surface adsorbed water molecules causes a slight weight loss for all fabricated films across the 50 o C − 135 o C temperature range [ 58 , 59 ]. The TGA curve of all films shows a weight loss of about 8.9%, which begins at 160°C and continues until 345°C. The weight loss was about 87.2% at 351 o C for all fabricated films due to the decomposition of the PMMA chain. The sample P 0 (PMMA) degrades completely at 388.18 o C, while samples P 1 , P 2 , and P 3 have different degradation temperatures at 390.27 o C, 391.35 o C, 391.87 o C, respectively. It can be observed that samples P 1 , P 2 , and P 3 have a higher degradation temperatures than sample P 0 . This improvement in degradation temperature of nanocomposites films with an increasing content of ZrO 2 nanofller is due to the intermolecular interaction of oxygen atoms of ZrO 2 nano-filler with methoxycarbonyl (C(O)OCH 3 ) group of PMMA chain [ 60 , 61 ]. The similar changes in thermal stability of PMMA-PVA-TiO 2 hybrid thin films were observed by Alsaad et al [ 62 ]. They have concluded that the strong intermolecular bonding between TiO 2 nanofillers and the polymer chain improved the thermal stability of PMMA-PVA-TiO 2 hybrid thin films with TiO 2 content. Our TGA results showed that increasing the ZrO 2 content in PMMA film improved its thermal stability and validated the successful incorporation of ZrO 2 nanofiller into the polymer chain. UV-Visible absorption spectroscopy UV-Visible absorption measurements were performed to determine the effect of ZrO 2 nanofiller concentration on the optical absorption of polymer nanocomposite films. Figure 5 shows the UV-Vis absorption spectrum for the samples P 0, P 1 , P 2 and P 3 . The absorption peak of sample P 0 is found at 218 nm and that of samples P 1 , P 2 and P 3 at 221 nm, 223 nm, and 227 nm, respectively, due to the π – π* electronic transition of an unsaturated carbonyl (C = O) group of PMMA, which was noticed in the FTIR spectra around at 1731 cm − 1 [ 63 , 64 ]. The small hump observed for all samples around at 280 nm is attributed to the n – π* transition induced by non-bonding electrons [ 65 , 66 ]. The absorption spectrum of sample P 0 becomes stable at higher wavelengths, indicating that pure PMMA is transparent over the visible region of the spectrum. The redshift of absorption onset of PMMA films with an increasing content of ZrO 2 nanofiller may be attributed to the occurrence of localized energy levels in the forbidden gap of matrix material and the formation of a charge transfer complex between PMMA and ZrO 2 nanofiller [ 67 ]. The energy band gap of samples is calculated using Tauc relation and is given by (αhν) n =A(hν - E g ) (3) where, α : absorption coefficient, hv : energy of photon, E g : energy gap and the value of 𝑛 depends on the nature of transition (for direct band gap n = 2 and indirect band gap n = 1/2). In Figs. 6 and 7 , we depict the Tauc plots for the direct and indirect band gap estimation of P 0 , P 1 , P 2 and P 3 samples. Table 3 displays the estimated values of the direct and indirect band gaps for the samples P 0 , P 1 , P 2 and P 3 . It is noticed that the reduction in values of direct and indirect band gap with an increasing the content of ZrO 2 nanofiller due to the formation of defects in the polymer matrix and the charge transfer complex between PMMA and ZrO 2 nanofiller. The occurrence of defects in PMMA matrix on the addition of ZrO 2 naofiller, which generates a localized energy levels in the band gap, lowers the materials band gap value [ 68 , 69 ]. Furthermore, as the content of nanofiller increases, the cross linking and dis-orderness of the polymer matrix increases, which cause the decrease in the value of band gap. Al-Bataineh et al [ 70 ] found a similar variation in the optical band gap of PMMA films with different nanofillers (ZnO, CuO, TiO 2 and SiO 2 ). The estimated values of direct and indirect band gaps are well consistent with previous published reports [ 71 – 73 ]. However, the obtained energy band gap values for the direct band transition are very close to those reported in earlier studies, indicating that the transition in PMMA/ZrO 2 nanocomposite films is direct in nature. Further, the additional study is required to better understand the nature of the band gap of PMMA/ZrO 2 nanocomposite films. Table 3 Calculated values of direct and indirect band gap of the samples. Sample Name Absorption edge (nm) Direct band gap (eV) Indirect band gap (eV) P 0 218 5.18 4.75 P 1 221 5.13 4.63 P 2 223 5.08 4.51 P 3 227 5.06 4.39 Photoluminescence spectroscopy The photoluminescence (PL) spectra of P 0 , P 1 , P 2 , and P 3 samples are depicted in Fig. 8 . The excitation wavelength is optimized and kept constant at 310 nm. Pure PMMA is a non-luminous material, and its luminescence behaviour is associated with electronic transitions and structural defects caused by polymer chain twisting and bending [ 66 , 74 ]. The broad PL emission peak observed at 433 nm for the sample P 0 can be attributed to the π – π* transition of carbonyl (C = O) group of PMMA matrix [ 75 ]. The PL peaks for samples P 1 , P 2 and P 3 are noted, respectively, at 437 nm, 442 nm, and 449 nm. A few less intense peaks are observed at lower wavelength around 380 nm for the P 1 , P 2 and P 3 samples and are ascribed to emission from the surface defects of ZrO 2 nanofiller [ 76 ]. The formation of charge transfer complexes between PMMA and ZrO 2 nanofiller as well as the generation of intermediate energy states within the band gap of PMMA matrix, results in a red shift in the PL peak. The appreciable increase in PL intensity of PMMA films with an increasing the content of ZrO 2 nanofiller is noticed. The molecular interaction between the electron donating groups of ZrO 2 and the electron withdrawing group (C = O) of PMMA matrix may increase the mobility of π electrons in the material and produce the single excitons. The radiative decay of a single exciton to the ground state increases PL intensity [ 77 , 78 ]. Rodrigues et al [ 79 ] observed a similar PL behaviour in carbon quantum dot embedded PMMA nanocomposite films fabricated using the solvent casting technique. They described the enhancement of PL intensity of PMMA films with the content of carbon quantum dot owing to the lower aggregation of quantum dots and the energy transfer process. The PL analysis of this study suggests the fabricated nanocomposite films possesses high PL intensity with an increase of ZrO 2 content. Mechanical properties To get insight into the effect of ZrO 2 nanofiller content on the tensile properties of PMMA/ZrO 2 nanocomposite films, tensile tests were carried out using universal testing machine. The stress-strain curves of P 0 , P 1 , P 2 and P 3 samples are shown in Fig. 9 , and the estimated parameters are given in Table 4 . The stress-strain curve of sample P 0 shows that the brittle failure intervenes before extensive plasticity. The enhancement of glassy behaviour for P 1 and P 2 sample upon addition of ZrO 2 nanofillers is due to the better intermolecular interaction between ZrO 2 nanofiller and PMMA chain [ 80 ]. The sample P 3 exhibits a value of strain failure that is 1.5 times lower than of P 1 and P 2 samples owing to the agglomeration/aggregation of nanofillers in the polymer matrix at higher concentration. The modification in mechanical properties of PMMA films with lower content of ZrO 2 nanofiller is due to the homogeneous distribution of nanofillers and better interaction between ZrO 2 nanofillers and PMMA matrix. However, at higher concentration of nanofillers, the mechanical parameters are reduced due to the agglomeration of ZrO 2 nanofillers. The agglomeration of ZrO 2 nanofillers due to the lower value of interface energy and a strong interactions, is well consistent with AFM images of sample. Yihun et al [ 81 ] observed the similar improvement in the mechanical toughness of SWNT/PMMA films. They elaborated that the strong interactions of PMMA with SMCNFs' were responsible for the improvement in mechanical strength. This mechanical investigation indicates the sample P 1 is better candidate for denture based application as it exhibits better mechanical properties and PL intensity. Table 4 Tensile properties of fabricated nanocomposite films. Sample Name Yield Stress (MPa) Yield Strain % Break Stress (MPa) Break Strain % Break Energy (MJ/m 3 ) P 0 1.96 0.156 0.930 0.066 1136 P 1 3.39 0.232 3.390 0.233 4665 P 2 2.89 0.240 2.530 0.196 2643 P 3 1.25 0.140 0.008 0.171 0907 Conclusion A series of PMMA/ZrO 2 nanocomposite films with different content of ZrO 2 nanofiller (3–10%) were fabricated by a solution casting technique. Effect of ZrO 2 nanofiller content on structural, optical and mechanical properties of fabricated nanocomposite films were investigated. XRD spectra reveal the formation of PMMA films and PMMA/ZrO 2 nanocomposite films. AFM images demonstrate the modification of surface roughness of nanocomposite films with an increasing concentration of ZrO 2 nanofiller due to the agglomeration of nano-fillers. The vibration modes of various functional groups of PMMA and PMMA/ZrO 2 nanocomposite films were confirmed through FTIR results. The enhancement of thermal stability of PMMA film with an increasing content of ZrO 2 nanofillers was noticed from TGA analysis. From band gap estimation, the reduction in band gap of PMMA films with an increase of ZrO 2 nanofiller content is noticed. PL studies showed that the enhancement of PL intensity of PMMA films with an increasing of content ZrO 2 nanofiller. The mechanical properties of PMMA films are altered significantly with an increase in ZrO 2 nanofiller. The composite with 3% of ZrO 2 nanofiller exhibits a superior mechanical properties with enhanced PL intensity and could be potential composite for denture based applications. Declarations Contributions of Authors: N.C.Horti: Methodology, Formal analysis, writing original draft and validation. S.I.Mathapati: data curation and editing. N.R.Banapurmath : conceptualization and review. V.S.Pujar: Formal analysis and data curation. S.R.Inamdar: review and editing. M.D.Kamatagi contributed to data curation, supervision, review and editing. Conflict of Interests: The authors declare no conflict of interest. Author Contribution N.C.Horti: Methodology, Formal analysis, writing original draft and validation. S.I.Mathapati: data curation and editing. N.R.Banapurmath : conceptualization and review. V.S.Pujar: Formal analysis and data curation. S.R.Inamdar: review and editing. 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Supplementary Files GraphicalAbstarct.png Cite Share Download PDF Status: Published Journal Publication published 28 Mar, 2025 Read the published version in Polymer Bulletin → Version 1 posted Editorial decision: Revision requested 28 Nov, 2024 Reviews received at journal 25 Aug, 2024 Reviewers agreed at journal 30 Jul, 2024 Reviewers invited by journal 30 Jul, 2024 Editor assigned by journal 18 Mar, 2024 Submission checks completed at journal 17 Mar, 2024 First submitted to journal 17 Mar, 2024 You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4115396","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":281431651,"identity":"c0a56dac-4947-4a61-a798-5d18b1f03d82","order_by":0,"name":"N. C. Horti","email":"","orcid":"","institution":"S.S. 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Pujari","email":"","orcid":"","institution":"Karnatak University","correspondingAuthor":false,"prefix":"","firstName":"V.","middleName":"S.","lastName":"Pujari","suffix":""},{"id":281431655,"identity":"7e2be407-152b-43f5-ae80-3d079fa21037","order_by":4,"name":"S. R. Inamdar","email":"","orcid":"","institution":"Karnatak University","correspondingAuthor":false,"prefix":"","firstName":"S.","middleName":"R.","lastName":"Inamdar","suffix":""},{"id":281431656,"identity":"923b2f1c-c630-4108-bc84-6122d1ca69b7","order_by":5,"name":"M. D. 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Government First Grade College and P.G Study Center","correspondingAuthor":true,"prefix":"","firstName":"M.","middleName":"D.","lastName":"Kamatagi","suffix":""}],"badges":[],"createdAt":"2024-03-17 04:29:18","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4115396/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4115396/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1007/s00289-025-05728-0","type":"published","date":"2025-03-28T15:57:23+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":53117869,"identity":"8e8a744d-d3d0-46ec-b638-225bac1cbce4","added_by":"auto","created_at":"2024-03-20 19:51:42","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":314277,"visible":true,"origin":"","legend":"\u003cp\u003eXRD spectrum of P\u003csub\u003e0, \u003c/sub\u003eP\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3 \u003c/sub\u003esamples\u003c/p\u003e","description":"","filename":"Fig1.png","url":"https://assets-eu.researchsquare.com/files/rs-4115396/v1/f77a7ca6279f67ae937d8ca1.png"},{"id":53117870,"identity":"c5bfa925-7448-4fba-8d92-d499e3177d8d","added_by":"auto","created_at":"2024-03-20 19:51:42","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":1353401,"visible":true,"origin":"","legend":"\u003cp\u003e3-D and 2-DAFM images of P\u003csub\u003e0, \u003c/sub\u003eP\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3 \u003c/sub\u003esamples\u003csub\u003e.\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"Fig2.png","url":"https://assets-eu.researchsquare.com/files/rs-4115396/v1/905ba8ed786841af9eb264ac.png"},{"id":53117871,"identity":"d1b599bc-af3b-4cf0-9651-a1bfbc84d36c","added_by":"auto","created_at":"2024-03-20 19:51:42","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":433383,"visible":true,"origin":"","legend":"\u003cp\u003eFTIR spectrum of the samples P\u003csub\u003e0, \u003c/sub\u003eP\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3.\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"Fig3.png","url":"https://assets-eu.researchsquare.com/files/rs-4115396/v1/0d79a24f116ae360c09e27c4.png"},{"id":53118584,"identity":"d0e8ff56-ed6d-4abf-8f0c-345ef6d3b623","added_by":"auto","created_at":"2024-03-20 19:59:43","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":151393,"visible":true,"origin":"","legend":"\u003cp\u003eThermal response curve of samples P\u003csub\u003e0, \u003c/sub\u003eP\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3.\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"Fig4.png","url":"https://assets-eu.researchsquare.com/files/rs-4115396/v1/c4c64ed8be0576a9b21dda69.png"},{"id":53117873,"identity":"2f048de3-f4a8-433f-b0c6-ce476cbf534b","added_by":"auto","created_at":"2024-03-20 19:51:43","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":209608,"visible":true,"origin":"","legend":"\u003cp\u003eAbsorption spectrum of the samples P\u003csub\u003e0\u003c/sub\u003e, P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3\u003c/sub\u003e.\u003c/p\u003e","description":"","filename":"Fig5.png","url":"https://assets-eu.researchsquare.com/files/rs-4115396/v1/2be5939724a10de05f0185a5.png"},{"id":53117874,"identity":"cd57b077-c534-4e01-b99a-faa87bd2e6ce","added_by":"auto","created_at":"2024-03-20 19:51:43","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":325834,"visible":true,"origin":"","legend":"\u003cp\u003eTauc plot for direct band gap transition of samples P\u003csub\u003e0\u003c/sub\u003e, P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3.\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"Fig6.png","url":"https://assets-eu.researchsquare.com/files/rs-4115396/v1/f8fe2399b3128cca39aa99ca.png"},{"id":53117877,"identity":"2858f170-a023-4e95-8dbe-59e23bf6371d","added_by":"auto","created_at":"2024-03-20 19:51:43","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":330594,"visible":true,"origin":"","legend":"\u003cp\u003eTauc plot for indirect band gap estimation of samples P\u003csub\u003e0\u003c/sub\u003e, P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3.\u003c/sub\u003e\u003c/p\u003e","description":"","filename":"Fig7.png","url":"https://assets-eu.researchsquare.com/files/rs-4115396/v1/7229db606d91a400bf942057.png"},{"id":53117878,"identity":"ea9fd5d2-a8b6-4d1c-b563-a60ac597f8d6","added_by":"auto","created_at":"2024-03-20 19:51:43","extension":"png","order_by":8,"title":"Figure 8","display":"","copyAsset":false,"role":"figure","size":231674,"visible":true,"origin":"","legend":"\u003cp\u003ePhotoluminescence spectrum of the P\u003csub\u003e0\u003c/sub\u003e, P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3 \u003c/sub\u003esamples.\u003c/p\u003e","description":"","filename":"Fig8.png","url":"https://assets-eu.researchsquare.com/files/rs-4115396/v1/efcb9a413b3e90606e08a6f4.png"},{"id":53117876,"identity":"a7c5b840-1cd2-4905-b3d6-04c130599c85","added_by":"auto","created_at":"2024-03-20 19:51:43","extension":"png","order_by":9,"title":"Figure 9","display":"","copyAsset":false,"role":"figure","size":194856,"visible":true,"origin":"","legend":"\u003cp\u003eTensile strain and stress curves of P\u003csub\u003e0\u003c/sub\u003e, P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3\u003c/sub\u003e samples.\u003c/p\u003e","description":"","filename":"Fig9.png","url":"https://assets-eu.researchsquare.com/files/rs-4115396/v1/2c87d1bb14277ac098866b3a.png"},{"id":79604839,"identity":"3cc263d1-5e52-4b56-89a8-559862120449","added_by":"auto","created_at":"2025-03-31 16:07:27","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":4442162,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4115396/v1/48880855-c5fa-4885-8403-acbf16e7ad17.pdf"},{"id":53118583,"identity":"10345c06-d447-4860-b8ce-7d432dac6412","added_by":"auto","created_at":"2024-03-20 19:59:42","extension":"png","order_by":1,"title":"","display":"","copyAsset":false,"role":"supplement","size":331079,"visible":true,"origin":"","legend":"","description":"","filename":"GraphicalAbstarct.png","url":"https://assets-eu.researchsquare.com/files/rs-4115396/v1/b80b757c5a253bb94b94620b.png"}],"financialInterests":"No competing interests reported.","formattedTitle":"Investigation of Structural, Optical and Mechanical Properties of Poly (methyl methacrylate) / Zirconium oxide (PMMA/ZrO2 ) Nanocomposite Films","fulltext":[{"header":"Introduction","content":"\u003cp\u003eThe design and fabrication of polymer/metal oxide nanocomposite films have gained considerable interest in recent years, owing to their novel optical, electrical, magnetic, and mechanical properties, as well as their widespread applications in the scientific, industrial, and medical fields [\u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e1\u003c/span\u003e, \u003cspan citationid=\"CR2\" class=\"CitationRef\"\u003e2\u003c/span\u003e]. The consistent distribution of nanofillers across the matrix, their enlarged interfacial area, and their interfacial interaction with the matrix materials can change these properties of the polymer nanocomposite films [\u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e3\u003c/span\u003e]. The homogeneous dispersion of nanofillers in the polymer matrix enhances loading efficiency and lowers local stress [\u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e4\u003c/span\u003e]. Furthermore, the particle size, shape, and concentration of nanofillers influence the properties of matrix material [\u003cspan citationid=\"CR5\" class=\"CitationRef\"\u003e5\u003c/span\u003e]. The concentration of nanofillers can have a significant impact on the various properties of nanocomposite films, including optical and mechanical properties. At higher nanofiller concentrations, the agglomeration/aggregation of nanofillers in the polymer matrix alters mechanical properties like low hardness, tensile modulus, and yield strength [\u003cspan citationid=\"CR6\" class=\"CitationRef\"\u003e6\u003c/span\u003e]. The addition of nanofillers generates new energy states in the matrix band gap, leading to an intriguing optical properties [\u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e7\u003c/span\u003e].\u003c/p\u003e \u003cp\u003ePolymers, namely polyaniline (PANI), polyvinylchloride (PVC), polythiophene (PTh), polycarbazole (PCz) and poly(methyl methacrylate) (PMMA) are being studied extensively for a wide range of applications including fuel cells, rechargeable batteries, corrosion resistance, optoelectronic devices, drug delivery, and medical applications [\u003cspan additionalcitationids=\"CR9 CR10\" citationid=\"CR8\" class=\"CitationRef\"\u003e8\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR11\" class=\"CitationRef\"\u003e11\u003c/span\u003e]. PMMA is more popular than other organic polymers due to its superior properties such as, good electrical insulators, good chemical resistance, high optical transparency, good weather ability and thermal stability [\u003cspan citationid=\"CR12\" class=\"CitationRef\"\u003e12\u003c/span\u003e, \u003cspan citationid=\"CR13\" class=\"CitationRef\"\u003e13\u003c/span\u003e]. It also has exceptional mechanical properties such as dimensional stability, impact resistance, flexural strength, and fracture toughness, making it better material for denture-based applications [\u003cspan citationid=\"CR14\" class=\"CitationRef\"\u003e14\u003c/span\u003e, \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e15\u003c/span\u003e]. In denture based application, the optical and mechanical properties play an important role. The addition of nanofillers such as metal, metal oxide, and carbon nanomaterials to polymer matrices can alter the opto-mechanical properties [\u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e16\u003c/span\u003e]. The series of metal oxides like SnO\u003csub\u003e2\u003c/sub\u003e, TiO\u003csub\u003e2\u003c/sub\u003e, MnO\u003csub\u003e2\u003c/sub\u003e and ZrO\u003csub\u003e2\u003c/sub\u003e have been used as filler materials in the polymer matrices due to their superior opto-mechanical properties [\u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e17\u003c/span\u003e, \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e18\u003c/span\u003e]. Among the numerous metal oxides, ZrO\u003csub\u003e2\u003c/sub\u003e is an unique choice due to its outstanding properties such as good ionic conductivity, high optical transparency, high facture toughness, good mechanical strength and wideband gap of \u0026gt;\u0026thinsp;5 eV[\u003cspan citationid=\"CR19\" class=\"CitationRef\"\u003e19\u003c/span\u003e, \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e20\u003c/span\u003e]. Because of these properties, ZrO\u003csub\u003e2\u003c/sub\u003e is a suitable filler material for the PMMA matrix to improve its optical and mechanical properties. Therefore, the fabrication of PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e nanocomposite films using different fabrication techniques such as sol-gel[\u003cspan citationid=\"CR21\" class=\"CitationRef\"\u003e21\u003c/span\u003e], spin coating[\u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e22\u003c/span\u003e], spray pyrolysis[\u003cspan citationid=\"CR23\" class=\"CitationRef\"\u003e23\u003c/span\u003e],magnetron sputtering[\u003cspan citationid=\"CR24\" class=\"CitationRef\"\u003e24\u003c/span\u003e], solution casting[\u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e25\u003c/span\u003e] were reported. Solution casting technique has several advantages over the other methods mentioned above, including its simplicity, low cost, and low operating temperature.\u003c/p\u003e \u003cp\u003eUntil now, numerous studies on the optical and mechanical properties of PMMA films with different types of nanofillers have been reported. They indicate the distinctive optical properties due to the formation of new states within the band gap of matrix material, as well as the enhancement/reduction of mechanical strength [\u003cspan citationid=\"CR26\" class=\"CitationRef\"\u003e26\u003c/span\u003e, \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e27\u003c/span\u003e]. Sengwa and Dhatarwal[\u003cspan citationid=\"CR28\" class=\"CitationRef\"\u003e28\u003c/span\u003e] used a solution casting technique with tetrahydrofuran as a solvent media to fabricate PMMA nanocomposite films with various nano-fillers (ZnO, SnO\u003csub\u003e2\u003c/sub\u003e and TiO\u003csub\u003e2\u003c/sub\u003e). Because of the formation of certain localized states in the PMMA forbidden energy gap caused by the generation of structural defects, they exhibited a shift in the absorption edge towards a longer wavelength and a decrease in the value of the energy band gap as the concentration of nano-filler increased. Tekin et al [\u003cspan citationid=\"CR29\" class=\"CitationRef\"\u003e29\u003c/span\u003e] utilized a simple spin coating technique to fabricate PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e and PMMA/WOxZrO\u003csub\u003e2\u003c/sub\u003e nano-comoposite films. They have observed the decrease in band gap of nanocomposite films as concentration of ZrO\u003csub\u003e2\u003c/sub\u003e nanoparticles increased due to increased carrier-carrier interaction, band levels approach of one another. By dissolving methyl methacrylate in chloroform and benzyl peroxide as a catalyst, a new spin casting technique was used to fabricate ZnO/PMMA nanocomposite films reported by Singh et al. [\u003cspan citationid=\"CR30\" class=\"CitationRef\"\u003e30\u003c/span\u003e]. The presence of intrinsic vacancies, such as Zn ions and oxygen vacancies, has been observed to produce blue-green emission peaks at 434 and 500 nm. The photoluminescence peak of ZnO/PMMA nanocomposite films has not significantly shifted due to the near band edge emission caused by band edge transitions or exciton recombination. Bay et al. [\u003cspan citationid=\"CR31\" class=\"CitationRef\"\u003e31\u003c/span\u003e] have reported the fabrication of PMMA/silica nanocomposite films by spin coting technique and examined the effects of free surfaces and internal interfaces on the mechanical properties of PMMA/silica nanocomposite films. As the thickness of the films increased, they observed a decrease in the stress value of PMMA films. However, there was no discernible change in the elastic modulus of the films when the concentration of nanoparticles loading increased. Mart\u0026iacute;nez et al [\u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e32\u003c/span\u003e] reported the mechanical and optical properties of PMMA-GPTMS-ZrO\u003csub\u003e2\u003c/sub\u003e hybrid thin films were fabricated through a sol-gel route. They elaborated the improvement in hardness of the PMMA-GPTMS-ZrO\u003csub\u003e2\u003c/sub\u003e hybrid films with ZrO\u003csub\u003e2\u003c/sub\u003e content due to the strong chemical bond between PMMA and ZrO\u003csub\u003e2\u003c/sub\u003e nanoparticles. The synthesis of PMMA-ZnO nanocomposites with different weight percent of ZnO nanoparticles (2\u0026ndash;5%) is reported by Ahmad et al [\u003cspan citationid=\"CR33\" class=\"CitationRef\"\u003e33\u003c/span\u003e]. In their investigation, they observed the enhancement in absorption intensity of PMMA-ZnO nanocomposites with weight percent of ZnO nanoparticles and the better antifungal efficacy against various candida species, indicating that this material could be a smart choice for denture application. Very recently, Kumari et al [\u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e34\u003c/span\u003e] developed the denture based PMMA and PMMA-ZrO\u003csub\u003e2\u003c/sub\u003e nanocomposites with different ZrO\u003csub\u003e2\u003c/sub\u003e content (2% -10%) using heat cure technique. They observed reduction of band gap as ZrO\u003csub\u003e2\u003c/sub\u003e content increases with the enhancement of mechanical properties for 5 wt % of ZrO\u003csub\u003e2\u003c/sub\u003e in PMMA including the maximum compressive strength (76.6 MPa) and fracture toughness (6.58 MPa-m\u003csup\u003e1/2\u003c/sup\u003e). Based on these results, they came to the conclusion that the 5 wt % of ZrO\u003csub\u003e2\u003c/sub\u003e nanoparticles loaded PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e nanocomposite is the better material for denture applications. A few studies on optical properties of PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e nanocomposite films have been reported in literature, however the variation in mechanical properties of PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e nanocomposite films with different concentration of ZrO\u003csub\u003e2\u003c/sub\u003e nanofillers have not been thoroughly investigated. The novelty of the present work involves PMMA a thermoplastic polymer that exhibits low mechanical strength and brittle on impact. Furthermore, the reinforcement of ZrO\u003csub\u003e2\u003c/sub\u003e nanofillers in PMMA matrix improves the mechanical rigidity and strength of the pure PMMA, rendering it a better alternative material for denture based applications. Therefore, in this work, we have fabricated PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e nanocomposite films using a solution casting method. The effect of varying concentrations of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller on the structural, optical and mechanical properties of PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e nanocomposite films is investigated.\u003c/p\u003e"},{"header":"Materials and method","content":"\u003cp\u003eZirconium sulphate (SRL chemicals), sodium hydroxide (SD fine), poly(methyl methacrylate) (Himedia Lab.Pvt.Ltd), chloroform (Molychem) of analytical grade are used without any refinement.\u003c/p\u003e \u003cdiv id=\"Sec3\" class=\"Section2\"\u003e \u003ch2\u003eFabrication of (PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e) Nanocomposite Films\u003c/h2\u003e \u003cp\u003eZrO\u003csub\u003e2\u003c/sub\u003e nanoparticles with a particle size of 10.78 nm were synthesized through a chemical co-precipitation method, as provided in reference [\u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e35\u003c/span\u003e]. Using a magnetic stirrer, 1 gram of poly (methyl methacrylate) (PMMA) was dissolved in 100 ml of chloroform during a standard fabrication procedure. 3%, 5%, and 10% (see Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e) of ZrO\u003csub\u003e2\u003c/sub\u003e nanoparticles were dispersed in 50 ml of chloroform. The obtained solution of ZrO\u003csub\u003e2\u003c/sub\u003e was mixed into the above PMMA solution drop wise, and the stirring was continued for 18 hours to complete the dispersion of ZrO\u003csub\u003e2\u003c/sub\u003e nanoparticles in the solution. Thereafter, the mixture was transferred into petri dish and allowed to slowly evaporate the solvent at room temperature for about 72 hours. Thereafter, a thin layer of nanocomposite was obtained. Finally, the solvent content and organic residues are removed from the obtained films by heating them for an hour at 60\u003csup\u003eo\u003c/sup\u003eC in a hot air oven. Here, we indicated the pure PMMA film as P\u003csub\u003e0\u003c/sub\u003e and the PMMA film with 3%, 5% and 10% of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller as P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e, and P\u003csub\u003e3\u003c/sub\u003e respectively.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eStoichiometric values for the fabrication of nanocomposite films.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"3\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample Name\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eWeight of PMMA (gm)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eWeight of ZrO\u003csub\u003e2\u003c/sub\u003e Nanofiller (gm)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e0\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1.0000\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.0000\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e1\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.9671\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.0309\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.9474\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.0526\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.8889\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.1111\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec4\" class=\"Section2\"\u003e \u003ch2\u003eCharacterization details\u003c/h2\u003e \u003cp\u003eX-ray diffraction pattern of nanocomposite films were recorded by Rigaku, Ultima-IV, X-ray diffractometer. To understand the formation and vibration of various functional groups of the fabricated nanocomposite films, an FTIR spectrophotometer (Nicolet-6900) was utilized. A thermogravimertic analyzer (DST Q600) was used to verify the thermal stability of nanocomposite films. UV-Vis absorption spectrophotometer (JASCO, V-670) and fluorescence emission spectrophotometer (HORIBA, Fluromax-4) were used to measure the optical properties of the nanocomposite films. A universal testing machine (UTM, 10ST) was used to examine the tensile and compressive strengths of the fabricated films.\u003c/p\u003e \u003c/div\u003e"},{"header":"Result and discussion","content":"\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e \u003ch2\u003eX-ray diffraction study\u003c/h2\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig1\" class=\"InternalRef\"\u003e1\u003c/span\u003e depicts the XRD pattern of samples P\u003csub\u003e0,\u003c/sub\u003e P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3\u003c/sub\u003e. The XRD pattern of sample P\u003csub\u003e0\u003c/sub\u003e reveals the broad intense peak at 15.23\u003csup\u003eo\u003c/sup\u003e is indexed to the (111) plane, while the less intense peak at an angle of 2θ\u0026thinsp;=\u0026thinsp;29.83\u003csup\u003eo\u003c/sup\u003e and 42.39\u003csup\u003eo\u003c/sup\u003e are corresponds to the (112) and (211) planes, respectively [\u003cspan citationid=\"CR36\" class=\"CitationRef\"\u003e36\u003c/span\u003e]. These three peaks in the XRD pattern show the formation of pure PMMA, and the broadness of diffraction peaks suggests the amorphous nature of PMMA [\u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e37\u003c/span\u003e, \u003cspan citationid=\"CR38\" class=\"CitationRef\"\u003e38\u003c/span\u003e]. The XRD pattern of P\u003csub\u003e1\u003c/sub\u003e and P\u003csub\u003e2\u003c/sub\u003e samples show the diffraction peaks of PMMA (shown by an asterisk) along with extra peaks at 2θ\u0026thinsp;=\u0026thinsp;30.15 \u003csup\u003eo\u003c/sup\u003e and 50.79\u003csup\u003eo\u003c/sup\u003e respectively, which could be indexed to the (101) and (112) crystal planes of the tetragonal ZrO\u003csub\u003e2\u003c/sub\u003e phase. From XRD pattern of P\u003csub\u003e3\u003c/sub\u003e sample, we have noticed the XRD peaks of PMMA along with peaks at 30.15\u003csup\u003eo\u003c/sup\u003e, 35.07\u003csup\u003eo\u003c/sup\u003e, 50.79\u003csup\u003eo\u003c/sup\u003e, and 60.69\u003csup\u003eo\u003c/sup\u003e respectively, corresponds to the (101) (110) (112) and (211) planes of the tetragonal ZrO\u003csub\u003e2\u003c/sub\u003e phase and is in according to the JCPDS data: 81-1455 [\u003cspan citationid=\"CR39\" class=\"CitationRef\"\u003e39\u003c/span\u003e]. The sample P\u003csub\u003e3\u003c/sub\u003e exhibits a reduction in the height of XRD peaks associated with PMMA, indicating a stronger interaction between the ZrO\u003csub\u003e2\u003c/sub\u003e nanofillers and PMMA matrix at higher ZrO\u003csub\u003e2\u003c/sub\u003e nano-filler content. This indicates that ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller is successfully incorporated into the PMMA matrix and the formation of PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e nanocomposite films.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec7\" class=\"Section2\"\u003e \u003ch2\u003eAtomic Force Microscopy\u003c/h2\u003e \u003cp\u003eThe surface topography of the fabricated films were analysed using Atomic Force Microscopy (AFM). The AFM instrument was operated in dynamic mode with vibration frequency of 150.487 kHz. Figure\u0026nbsp;\u003cspan refid=\"Fig2\" class=\"InternalRef\"\u003e2\u003c/span\u003e shows the 3-D and 2-D AFM images of P\u003csub\u003e0,\u003c/sub\u003e P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3\u003c/sub\u003e samples. The AFM image of sample P\u003csub\u003e0\u003c/sub\u003e shows the peaks of different heights with small irregularities indicates the grains are oriented randomly. Whereas, the change in surface irregularities for the samples P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3\u003c/sub\u003e is due to the agglomeration of ZrO\u003csub\u003e2\u003c/sub\u003e nanofillers. This change in agglomeration rate with concentration of ZrO\u003csub\u003e2\u003c/sub\u003e nanofillers is caused by the lower interfacial energy and the variation of interfacial interaction of oxygen atom of ZrO\u003csub\u003e2\u003c/sub\u003e nanofillers and methoxycarbonyl (C(O)OCH\u003csub\u003e3\u003c/sub\u003e) group of PMMA chain. The average surface roughness (S\u003csub\u003eavr\u003c/sub\u003e) and root mean square of surface roughness (S\u003csub\u003erms\u003c/sub\u003e) of fabricated nanocomposite films was estimated by following formulae [\u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e40\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003cdiv id=\"Equ1\" class=\"Equation\"\u003e \u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e\n$${S}_{avr}= \\frac{1}{MN}\\sum _{k=0}^{M-1}\\sum _{i=0}^{n-1}\\left|z({x}_{k}-{y}_{i})\\right|$$\u003c/div\u003e \u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eand\u003cdiv id=\"Equ2\" class=\"Equation\"\u003e\u003cdiv format=\"TEX\" class=\"mathdisplay\" id=\"FileID_Equ2\" name=\"EquationSource\"\u003e\n$${S}_{rms}= \\sqrt{\\frac{1}{MN}\\sum _{k=0}^{M-1}\\sum _{i=0}^{n-1}{\\left[z({x}_{k}-{y}_{i}\\right]}^{2}}$$\u003c/div\u003e\u003cdiv class=\"EquationNumber\"\u003e2\u003c/div\u003e\u003c/div\u003e\u003c/p\u003e \u003cp\u003eThe estimated values of average surface roughness and root mean square of surface roughness of fabricated nanocomposite films are listed in Table \u003cspan refid=\"Tab2\" class=\"InternalRef\"\u003e2\u003c/span\u003e. It is observed that as the concentration of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller increases, the values of S\u003csub\u003eavr\u003c/sub\u003e and S\u003csub\u003erms\u003c/sub\u003e of nanocomposite films decreases due to the agglomeration of nanofillers. An increase of nanofiller concentration results in a decrease of interface energy and a stronger interaction. This accelerates the agglomeration rate of nanocomposite films, facilitating the growth of continuous layers and possibly reducing the surface roughness of nanocomposite films [\u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e41\u003c/span\u003e].\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab2\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 2\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eEstimated values for the roughness of nanocomposite films.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"3\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample Name\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eS\u003csub\u003ea\u003c/sub\u003e(\u0026micro;m)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eS\u003csub\u003erms\u003c/sub\u003e(\u0026micro;m)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e0\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.326\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.570\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e1\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.135\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.367\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.083\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.288\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e0.020\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.141\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec8\" class=\"Section2\"\u003e \u003ch2\u003eFourier Transform Infrared spectroscopy\u003c/h2\u003e \u003cp\u003eThe FTIR spectra of samples P\u003csub\u003e0,\u003c/sub\u003e P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3\u003c/sub\u003e are displayed in Fig.\u0026nbsp;\u003cspan refid=\"Fig3\" class=\"InternalRef\"\u003e3\u003c/span\u003e. In the FTIR spectrum of P\u003csub\u003e0\u003c/sub\u003e samples, the band at 481 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e appears due to the C\u0026ndash;C in plane bonding and the band at 665 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is due to the stretching vibration of the C-C\u0026thinsp;=\u0026thinsp;O group [\u003cspan citationid=\"CR42\" class=\"CitationRef\"\u003e42\u003c/span\u003e, \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e43\u003c/span\u003e]. The band noticed at 758 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is attributed to the C \u0026ndash; C skeletal mode and the sharp band at 841 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e correspond to the CH\u003csub\u003e2\u003c/sub\u003e rocking vibration [\u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e44\u003c/span\u003e, \u003cspan citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e]. The bands centred at 989 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 1386 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are assigned to the C-O-C stretching vibration and the deformation of O-CH\u003csub\u003e3\u003c/sub\u003e groups [\u003cspan additionalcitationids=\"CR46\" citationid=\"CR45\" class=\"CitationRef\"\u003e45\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e47\u003c/span\u003e]. The band noticed at 1455 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is ascribed to the asymmetric bending vibration of methyl (-CH\u003csub\u003e3\u003c/sub\u003e) group [\u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e48\u003c/span\u003e]. The sharp band that appeared around at 1731 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is because of the symmetric carbonyl (C\u0026thinsp;=\u0026thinsp;O) stretching of ester group, which confirms the formation of PMMA [\u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e49\u003c/span\u003e, \u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e50\u003c/span\u003e]. The band found at 2843 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e is related to the symmetric stretching vibration of CH group [\u003cspan citationid=\"CR51\" class=\"CitationRef\"\u003e51\u003c/span\u003e]. The strong bands identified at 2943 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 2996 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are associated with the antisymmetric vibration of CH\u003csub\u003e3\u003c/sub\u003e and CH\u003csub\u003e2\u003c/sub\u003e groups [\u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e52\u003c/span\u003e]. The bands at 3439 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 3552 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e and 3623 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e are ascribed to the stretching vibration of C-H group [\u003cspan citationid=\"CR53\" class=\"CitationRef\"\u003e53\u003c/span\u003e]. FTIR spectrum of sample P\u003csub\u003e0\u003c/sub\u003e is consistent with other reports [\u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e54\u003c/span\u003e, \u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e55\u003c/span\u003e]. From FTIR spectrum of samples P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3\u003c/sub\u003e, we noticed the peaks of PMMA with a small hump around at 553 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e (indicated by circle) and is ascribed to the stretching vibration of Zr-O groups of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller [\u003cspan citationid=\"CR56\" class=\"CitationRef\"\u003e56\u003c/span\u003e]. The small shift of bands at 726 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e, 827 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003eand 1487 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e correspond to the CH and CH\u003csub\u003e3\u003c/sub\u003e stretching vibration, indicates the good interaction of oxygen atom of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller with PMMA matrix via methoxycarbonyl (C(O)OCH\u003csub\u003e3\u003c/sub\u003e)group [\u003cspan citationid=\"CR57\" class=\"CitationRef\"\u003e57\u003c/span\u003e]. FTIR results confirm the better interaction of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller with PMMA matrix and the successful incorporation of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller into PMMA matrix.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec9\" class=\"Section2\"\u003e \u003ch2\u003eThermogravimetric analysis\u003c/h2\u003e \u003cp\u003e \u003cdiv class=\"BlockQuote\"\u003e \u003cp\u003eFigure \u003cspan refid=\"Fig4\" class=\"InternalRef\"\u003e4\u003c/span\u003e depicts the result of thermogravimetric analysis (TGA) which is used to assess the thermal stability of fabricated nanocomposite films. The evaporation of solvents and surface adsorbed water molecules causes a slight weight loss for all fabricated films across the 50\u003csup\u003eo\u003c/sup\u003eC \u0026minus;\u0026thinsp;135\u003csup\u003eo\u003c/sup\u003eC temperature range [\u003cspan citationid=\"CR58\" class=\"CitationRef\"\u003e58\u003c/span\u003e, \u003cspan citationid=\"CR59\" class=\"CitationRef\"\u003e59\u003c/span\u003e]. The TGA curve of all films shows a weight loss of about 8.9%, which begins at 160\u0026deg;C and continues until 345\u0026deg;C. The weight loss was about 87.2% at 351\u003csup\u003eo\u003c/sup\u003eC for all fabricated films due to the decomposition of the PMMA chain. The sample P\u003csub\u003e0\u003c/sub\u003e (PMMA) degrades completely at 388.18\u003csup\u003eo\u003c/sup\u003eC, while samples P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e, and P\u003csub\u003e3\u003c/sub\u003e have different degradation temperatures at 390.27\u003csup\u003eo\u003c/sup\u003eC, 391.35\u003csup\u003eo\u003c/sup\u003eC, 391.87\u003csup\u003eo\u003c/sup\u003eC, respectively. It can be observed that samples P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e, and P\u003csub\u003e3\u003c/sub\u003e have a higher degradation temperatures than sample P\u003csub\u003e0\u003c/sub\u003e. This improvement in degradation temperature of nanocomposites films with an increasing content of ZrO\u003csub\u003e2\u003c/sub\u003e nanofller is due to the intermolecular interaction of oxygen atoms of ZrO\u003csub\u003e2\u003c/sub\u003e nano-filler with methoxycarbonyl (C(O)OCH\u003csub\u003e3\u003c/sub\u003e) group of PMMA chain [\u003cspan citationid=\"CR60\" class=\"CitationRef\"\u003e60\u003c/span\u003e, \u003cspan citationid=\"CR61\" class=\"CitationRef\"\u003e61\u003c/span\u003e]. The similar changes in thermal stability of PMMA-PVA-TiO\u003csub\u003e2\u003c/sub\u003e hybrid thin films were observed by Alsaad et al [\u003cspan citationid=\"CR62\" class=\"CitationRef\"\u003e62\u003c/span\u003e]. They have concluded that the strong intermolecular bonding between TiO\u003csub\u003e2\u003c/sub\u003e nanofillers and the polymer chain improved the thermal stability of PMMA-PVA-TiO\u003csub\u003e2\u003c/sub\u003e hybrid thin films with TiO\u003csub\u003e2\u003c/sub\u003e content. Our TGA results showed that increasing the ZrO\u003csub\u003e2\u003c/sub\u003e content in PMMA film improved its thermal stability and validated the successful incorporation of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller into the polymer chain.\u003c/p\u003e \u003c/div\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec10\" class=\"Section2\"\u003e \u003ch2\u003eUV-Visible absorption spectroscopy\u003c/h2\u003e \u003cp\u003eUV-Visible absorption measurements were performed to determine the effect of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller concentration on the optical absorption of polymer nanocomposite films. Figure\u0026nbsp;\u003cspan refid=\"Fig5\" class=\"InternalRef\"\u003e5\u003c/span\u003e shows the UV-Vis absorption spectrum for the samples P\u003csub\u003e0,\u003c/sub\u003e P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3\u003c/sub\u003e. The absorption peak of sample P\u003csub\u003e0\u003c/sub\u003e is found at 218 nm and that of samples P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3\u003c/sub\u003e at 221 nm, 223 nm, and 227 nm, respectively, due to the π \u0026ndash; π* electronic transition of an unsaturated carbonyl (C\u0026thinsp;=\u0026thinsp;O) group of PMMA, which was noticed in the FTIR spectra around at 1731 cm\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e[\u003cspan citationid=\"CR63\" class=\"CitationRef\"\u003e63\u003c/span\u003e, \u003cspan citationid=\"CR64\" class=\"CitationRef\"\u003e64\u003c/span\u003e]. The small hump observed for all samples around at 280 nm is attributed to the n \u0026ndash; π* transition induced by non-bonding electrons [\u003cspan citationid=\"CR65\" class=\"CitationRef\"\u003e65\u003c/span\u003e, \u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e66\u003c/span\u003e]. The absorption spectrum of sample P\u003csub\u003e0\u003c/sub\u003e becomes stable at higher wavelengths, indicating that pure PMMA is transparent over the visible region of the spectrum. The redshift of absorption onset of PMMA films with an increasing content of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller may be attributed to the occurrence of localized energy levels in the forbidden gap of matrix material and the formation of a charge transfer complex between PMMA and ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller [\u003cspan citationid=\"CR67\" class=\"CitationRef\"\u003e67\u003c/span\u003e]. The energy band gap of samples is calculated using Tauc relation and is given by\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e(αhν)\u003csup\u003en\u003c/sup\u003e =A(hν - E\u003csub\u003eg\u003c/sub\u003e) (3)\u003c/p\u003e \u003cp\u003ewhere, α : absorption coefficient, \u003cem\u003ehv\u003c/em\u003e: energy of photon, \u003cem\u003eE\u003c/em\u003e\u003csub\u003e\u003cem\u003eg\u003c/em\u003e\u003c/sub\u003e : energy gap and the value of \u0026#119899; depends on the nature of transition (for direct band gap n\u0026thinsp;=\u0026thinsp;2 and indirect band gap n\u0026thinsp;=\u0026thinsp;1/2). In Figs.\u0026nbsp;\u003cspan refid=\"Fig6\" class=\"InternalRef\"\u003e6\u003c/span\u003e and \u003cspan refid=\"Fig7\" class=\"InternalRef\"\u003e7\u003c/span\u003e, we depict the Tauc plots for the direct and indirect band gap estimation of P\u003csub\u003e0\u003c/sub\u003e, P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3\u003c/sub\u003e samples. Table\u0026nbsp;\u003cspan refid=\"Tab3\" class=\"InternalRef\"\u003e3\u003c/span\u003e displays the estimated values of the direct and indirect band gaps for the samples P\u003csub\u003e0\u003c/sub\u003e, P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3\u003c/sub\u003e. It is noticed that the reduction in values of direct and indirect band gap with an increasing the content of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller due to the formation of defects in the polymer matrix and the charge transfer complex between PMMA and ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller. The occurrence of defects in PMMA matrix on the addition of ZrO\u003csub\u003e2\u003c/sub\u003e naofiller, which generates a localized energy levels in the band gap, lowers the materials band gap value [\u003cspan citationid=\"CR68\" class=\"CitationRef\"\u003e68\u003c/span\u003e, \u003cspan citationid=\"CR69\" class=\"CitationRef\"\u003e69\u003c/span\u003e]. Furthermore, as the content of nanofiller increases, the cross linking and dis-orderness of the polymer matrix increases, which cause the decrease in the value of band gap. Al-Bataineh et al [\u003cspan citationid=\"CR70\" class=\"CitationRef\"\u003e70\u003c/span\u003e] found a similar variation in the optical band gap of PMMA films with different nanofillers (ZnO, CuO, TiO\u003csub\u003e2\u003c/sub\u003e and SiO\u003csub\u003e2\u003c/sub\u003e). The estimated values of direct and indirect band gaps are well consistent with previous published reports [\u003cspan additionalcitationids=\"CR72\" citationid=\"CR71\" class=\"CitationRef\"\u003e71\u003c/span\u003e\u0026ndash;\u003cspan citationid=\"CR73\" class=\"CitationRef\"\u003e73\u003c/span\u003e]. However, the obtained energy band gap values for the direct band transition are very close to those reported in earlier studies, indicating that the transition in PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e nanocomposite films is direct in nature. Further, the additional study is required to better understand the nature of the band gap of PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e nanocomposite films.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab3\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eCalculated values of direct and indirect band gap of the samples.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample Name\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eAbsorption edge (nm)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eDirect band gap (eV)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eIndirect band gap (eV)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e0\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e218\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e5.18\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e4.75\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e1\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e221\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e5.13\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e4.63\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e223\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e5.08\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e4.51\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e227\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e5.06\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e4.39\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec11\" class=\"Section2\"\u003e \u003ch2\u003ePhotoluminescence spectroscopy\u003c/h2\u003e \u003cp\u003eThe photoluminescence (PL) spectra of P\u003csub\u003e0\u003c/sub\u003e, P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e, and P\u003csub\u003e3\u003c/sub\u003e samples are depicted in Fig.\u0026nbsp;\u003cspan refid=\"Fig8\" class=\"InternalRef\"\u003e8\u003c/span\u003e. The excitation wavelength is optimized and kept constant at 310 nm. Pure PMMA is a non-luminous material, and its luminescence behaviour is associated with electronic transitions and structural defects caused by polymer chain twisting and bending [\u003cspan citationid=\"CR66\" class=\"CitationRef\"\u003e66\u003c/span\u003e, \u003cspan citationid=\"CR74\" class=\"CitationRef\"\u003e74\u003c/span\u003e]. The broad PL emission peak observed at 433 nm for the sample P\u003csub\u003e0\u003c/sub\u003e can be attributed to the π \u0026ndash; π* transition of carbonyl (C\u0026thinsp;=\u0026thinsp;O) group of PMMA matrix [\u003cspan citationid=\"CR75\" class=\"CitationRef\"\u003e75\u003c/span\u003e]. The PL peaks for samples P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3\u003c/sub\u003e are noted, respectively, at 437 nm, 442 nm, and 449 nm. A few less intense peaks are observed at lower wavelength around 380 nm for the P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3\u003c/sub\u003e samples and are ascribed to emission from the surface defects of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller [\u003cspan citationid=\"CR76\" class=\"CitationRef\"\u003e76\u003c/span\u003e]. The formation of charge transfer complexes between PMMA and ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller as well as the generation of intermediate energy states within the band gap of PMMA matrix, results in a red shift in the PL peak. The appreciable increase in PL intensity of PMMA films with an increasing the content of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller is noticed. The molecular interaction between the electron donating groups of ZrO\u003csub\u003e2\u003c/sub\u003e and the electron withdrawing group (C\u0026thinsp;=\u0026thinsp;O) of PMMA matrix may increase the mobility of π electrons in the material and produce the single excitons. The radiative decay of a single exciton to the ground state increases PL intensity [\u003cspan citationid=\"CR77\" class=\"CitationRef\"\u003e77\u003c/span\u003e, \u003cspan citationid=\"CR78\" class=\"CitationRef\"\u003e78\u003c/span\u003e]. Rodrigues et al [\u003cspan citationid=\"CR79\" class=\"CitationRef\"\u003e79\u003c/span\u003e] observed a similar PL behaviour in carbon quantum dot embedded PMMA nanocomposite films fabricated using the solvent casting technique. They described the enhancement of PL intensity of PMMA films with the content of carbon quantum dot owing to the lower aggregation of quantum dots and the energy transfer process. The PL analysis of this study suggests the fabricated nanocomposite films possesses high PL intensity with an increase of ZrO\u003csub\u003e2\u003c/sub\u003e content.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003c/div\u003e \u003cdiv id=\"Sec12\" class=\"Section2\"\u003e \u003ch2\u003eMechanical properties\u003c/h2\u003e \u003cp\u003eTo get insight into the effect of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller content on the tensile properties of PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e nanocomposite films, tensile tests were carried out using universal testing machine. The stress-strain curves of P\u003csub\u003e0\u003c/sub\u003e, P\u003csub\u003e1\u003c/sub\u003e, P\u003csub\u003e2\u003c/sub\u003e and P\u003csub\u003e3\u003c/sub\u003e samples are shown in Fig.\u0026nbsp;\u003cspan refid=\"Fig9\" class=\"InternalRef\"\u003e9\u003c/span\u003e, and the estimated parameters are given in Table \u003cspan refid=\"Tab4\" class=\"InternalRef\"\u003e4\u003c/span\u003e. The stress-strain curve of sample P\u003csub\u003e0\u003c/sub\u003e shows that the brittle failure intervenes before extensive plasticity. The enhancement of glassy behaviour for P\u003csub\u003e1\u003c/sub\u003e and P\u003csub\u003e2\u003c/sub\u003e sample upon addition of ZrO\u003csub\u003e2\u003c/sub\u003e nanofillers is due to the better intermolecular interaction between ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller and PMMA chain [\u003cspan citationid=\"CR80\" class=\"CitationRef\"\u003e80\u003c/span\u003e]. The sample P\u003csub\u003e3\u003c/sub\u003e exhibits a value of strain failure that is 1.5 times lower than of P\u003csub\u003e1\u003c/sub\u003e and P\u003csub\u003e2\u003c/sub\u003e samples owing to the agglomeration/aggregation of nanofillers in the polymer matrix at higher concentration. The modification in mechanical properties of PMMA films with lower content of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller is due to the homogeneous distribution of nanofillers and better interaction between ZrO\u003csub\u003e2\u003c/sub\u003e nanofillers and PMMA matrix. However, at higher concentration of nanofillers, the mechanical parameters are reduced due to the agglomeration of ZrO\u003csub\u003e2\u003c/sub\u003e nanofillers. The agglomeration of ZrO\u003csub\u003e2\u003c/sub\u003e nanofillers due to the lower value of interface energy and a strong interactions, is well consistent with AFM images of sample. Yihun et al [\u003cspan citationid=\"CR81\" class=\"CitationRef\"\u003e81\u003c/span\u003e] observed the similar improvement in the mechanical toughness of SWNT/PMMA films. They elaborated that the strong interactions of PMMA with SMCNFs' were responsible for the improvement in mechanical strength. This mechanical investigation indicates the sample P\u003csub\u003e1\u003c/sub\u003e is better candidate for denture based application as it exhibits better mechanical properties and PL intensity.\u003c/p\u003e \u003cp\u003e \u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab4\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eTensile properties of fabricated nanocomposite films.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"6\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c5\" colnum=\"5\"\u003e\u003c/div\u003e \u003cdiv align=\"char\" char=\".\" class=\"colspec\" colname=\"c6\" colnum=\"6\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eSample Name\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003eYield Stress (MPa)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eYield Strain %\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eBreak Stress (MPa)\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c5\"\u003e \u003cp\u003eBreak Strain %\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c6\"\u003e \u003cp\u003eBreak Energy\u003c/p\u003e \u003cp\u003e(MJ/m\u003csup\u003e3\u003c/sup\u003e)\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e0\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1.96\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.156\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.930\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.066\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e1136\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e1\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e3.39\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.232\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e3.390\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.233\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e4665\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e2\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e2.89\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.240\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e2.530\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.196\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e2643\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003e\u003cb\u003eP\u003c/b\u003e\u003csub\u003e\u003cb\u003e3\u003c/b\u003e\u003c/sub\u003e\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c2\"\u003e \u003cp\u003e1.25\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c3\"\u003e \u003cp\u003e0.140\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c4\"\u003e \u003cp\u003e0.008\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c5\"\u003e \u003cp\u003e0.171\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"char\" char=\".\" colname=\"c6\"\u003e \u003cp\u003e0907\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003c/div\u003e"},{"header":"Conclusion","content":"\u003cp\u003eA series of PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e nanocomposite films with different content of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller (3\u0026ndash;10%) were fabricated by a solution casting technique. Effect of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller content on structural, optical and mechanical properties of fabricated nanocomposite films were investigated. XRD spectra reveal the formation of PMMA films and PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e nanocomposite films. AFM images demonstrate the modification of surface roughness of nanocomposite films with an increasing concentration of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller due to the agglomeration of nano-fillers. The vibration modes of various functional groups of PMMA and PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e nanocomposite films were confirmed through FTIR results. The enhancement of thermal stability of PMMA film with an increasing content of ZrO\u003csub\u003e2\u003c/sub\u003e nanofillers was noticed from TGA analysis. From band gap estimation, the reduction in band gap of PMMA films with an increase of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller content is noticed. PL studies showed that the enhancement of PL intensity of PMMA films with an increasing of content ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller. The mechanical properties of PMMA films are altered significantly with an increase in ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller. The composite with 3% of ZrO\u003csub\u003e2\u003c/sub\u003e nanofiller exhibits a superior mechanical properties with enhanced PL intensity and could be potential composite for denture based applications.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e \u003ch2\u003eContributions of Authors:\u003c/h2\u003e \u003cp\u003eN.C.Horti: Methodology, Formal analysis, writing original draft and validation. S.I.Mathapati: data curation and editing. N.R.Banapurmath : conceptualization and review. V.S.Pujar: Formal analysis and data curation. S.R.Inamdar: review and editing. M.D.Kamatagi contributed to data curation, supervision, review and editing.\u003c/p\u003e \u003c/p\u003e\u003cp\u003e \u003ch2\u003eConflict of Interests:\u003c/h2\u003e \u003cp\u003eThe authors declare no conflict of interest.\u003c/p\u003e \u003c/p\u003e\u003ch2\u003eAuthor Contribution\u003c/h2\u003e\u003cp\u003eN.C.Horti: Methodology, Formal analysis, writing original draft and validation. S.I.Mathapati: data curation and editing. N.R.Banapurmath : conceptualization and review. V.S.Pujar: Formal analysis and data curation. S.R.Inamdar: review and editing. M.D.Kamatagi contributed to data curation, supervision, review and editing.\u003c/p\u003e\u003ch2\u003eAcknowledgements:\u003c/h2\u003e \u003cp\u003eThis work is supported by University Grants Commission (UGC), India.\u003c/p\u003e\u003ch2\u003eData Availability Statement:\u003c/h2\u003e \u003cp\u003eThe data that support the findings of this study are available from the corresponding author upon reasonable request.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\u003cli\u003e\u003cspan\u003eAlsaad AM, Ahmad AA, Al Dairy AR, Al-anbar AS, Al-Bataineh QM (2020) Spectroscopic characterization of optical and thermal properties of (PMMA-PVA) hybrid thin films doped with SiO\u003csub\u003e2\u003c/sub\u003e nanoparticles. 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Polymer 197:122497\u003c/span\u003e\u003c/li\u003e\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"polymer-bulletin","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"pobu","sideBox":"Learn more about [Polymer Bulletin](http://link.springer.com/journal/289)","snPcode":"289","submissionUrl":"https://submission.nature.com/new-submission/289/3","title":"Polymer Bulletin","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false},"keywords":"PMMA, ZrO2, Nanocomposite Films, Solution casting, Optical and mechanical properties","lastPublishedDoi":"10.21203/rs.3.rs-4115396/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4115396/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThis research article explain the fabrication of poly (methyl methacrylate)/ zirconium oxide (PMMA/ZrO\u003csub\u003e2\u003c/sub\u003e) nanocomposite films via a solution casting technique. The fabricated nanocomposite films were examined for their structural, morphological and optical properties through X-ray diffraction, Atomic force microscopy, Fourier infrared transform, UV-Vis absorption and fluorescence emission spectroscopy techniques. Thermogravimetric test was performed to check the thermal stability of nanocomposite films and the mechanical properties was assessed using a universal testing machine. XRD patterns of samples showed the formation of pure PMMA films and the successful incorporation of ZrO\u003csub\u003e2 \u003c/sub\u003enano-fillers into polymer matrix and the results are in good agreement with the FTIR results. The agglomeration of particles and change in surface roughness of films was noticed from AFM images. UV-Vis absorption analysis revealed that the absorption onset of PMMA films shifted towards a longer wavelength with an increasing content of ZrO\u003csub\u003e2 \u003c/sub\u003enano-fillers. The photoluminescence spectra exhibited the significant enhancement of photoluminescence intensity and a red shift in the emission peak of PMMA films as the content of ZrO\u003csub\u003e2 \u003c/sub\u003enanofillers increases. With an increase of ZrO\u003csub\u003e2 \u003c/sub\u003enanofiller concentration, the mechanical properties of composite films change significantly. The sample with 3% nano-filler exhibited the good mechanical strength, including a break energy of 4665 MJ/m\u003csup\u003e3 \u003c/sup\u003eand a break stress of 3.390 MPa and superior photoluminescence intensity making it suitable composite material for denture-based applications.\u003c/p\u003e","manuscriptTitle":"Investigation of Structural, Optical and Mechanical Properties of Poly (methyl methacrylate) / Zirconium oxide (PMMA/ZrO2 ) Nanocomposite Films","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-03-20 19:51:37","doi":"10.21203/rs.3.rs-4115396/v1","editorialEvents":[{"type":"communityComments","content":0},{"type":"decision","content":"Revision requested","date":"2024-11-28T08:56:24+00:00","index":"","fulltext":""},{"type":"editorInvitedReview","content":"","date":"2024-08-25T20:12:42+00:00","index":"hide","fulltext":""},{"type":"reviewerAgreed","content":"226369750040413750081192836639645511163","date":"2024-07-30T18:51:38+00:00","index":"hide","fulltext":""},{"type":"reviewersInvited","content":"","date":"2024-07-30T15:23:31+00:00","index":"","fulltext":""},{"type":"editorAssigned","content":"","date":"2024-03-18T07:52:15+00:00","index":"","fulltext":""},{"type":"checksComplete","content":"","date":"2024-03-18T01:41:31+00:00","index":"","fulltext":""},{"type":"submitted","content":"Polymer Bulletin","date":"2024-03-17T04:24:46+00:00","index":"","fulltext":""}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"polymer-bulletin","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":false,"externalIdentity":"pobu","sideBox":"Learn more about [Polymer Bulletin](http://link.springer.com/journal/289)","snPcode":"289","submissionUrl":"https://submission.nature.com/new-submission/289/3","title":"Polymer Bulletin","twitterHandle":"","acdcEnabled":true,"dfaEnabled":true,"editorialSystem":"stoa","reportingPortfolio":"Springer Hybrid","inReviewEnabled":true,"inReviewRevisionsEnabled":false}}],"origin":"","ownerIdentity":"b78a4bf1-c7c0-41aa-ab02-4e53a3ae9ec1","owner":[],"postedDate":"March 20th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2025-03-31T16:00:42+00:00","versionOfRecord":{"articleIdentity":"rs-4115396","link":"https://doi.org/10.1007/s00289-025-05728-0","journal":{"identity":"polymer-bulletin","isVorOnly":false,"title":"Polymer Bulletin"},"publishedOn":"2025-03-28 15:57:23","publishedOnDateReadable":"March 28th, 2025"},"versionCreatedAt":"2024-03-20 19:51:37","video":"","vorDoi":"10.1007/s00289-025-05728-0","vorDoiUrl":"https://doi.org/10.1007/s00289-025-05728-0","workflowStages":[]},"version":"v1","identity":"rs-4115396","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4115396","identity":"rs-4115396","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}