Spectroscopic, Thermal and Electrical Properties of CNT Added PVC/PMMA Blends

doi:10.21203/rs.3.rs-4706900/v1

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Spectroscopic, Thermal and Electrical Properties of CNT Added PVC/PMMA Blends

https://doi.org/10.21203/rs.3.rs-4706900/v1

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This study investigated the effect of different ratios of CNT (carbon nanotube) additive on various properties of PVC/PMMA (poly (vinyl chloride/poly(methyl methacrylate)) blend. For this purpose, a nanocomposite was prepared by adding 0, 0.1, 0.5, and 1% CNT (carbon nanotube) to the PVC/PMMA blend, which was prepared by casting technique from a common solvent. Spectroscopic and thermal analyses were carried out on the prepared nanocomposite samples. SEM imaging showed that CNTs showed good distribution and interaction in the polymer matrix. XRD analyses showed the amorphous character of the structure, and CNT doping did not create any significant changes in crystallinity. The highest crystallinity was found in PVC40-1 at 15.24%. All the samples had similar Tg (Glass transition Temperature) values in the DSC analysis. The existence of CNT did not affect Tg values. CNTs helped to preserve the integrity of nanocomposite because the rate of degradation of nanocomposite without CNT reached its highest values (258.95–514.19W/min) in the DTG. TGA analysis showed that all the weight loss curves of the samples looked similar. Weight loss occurred at 194, 249, and 442°C and all of them were very similar. CNTs did not change the electrical conductivity of the nanocomposite. A fragility was observed in the structure of the nanocomposite.

PVC

PMMA

CNT

Blend

nanocomposite

A polymer blend is a physical mixture made of two or more polymers to obtain a new material with different physical properties. As part of replacing traditional polymers, the production of polymer blends represents the possible properties of all plastics produced in 2010.

The construction and commercial restraint of the new polymer often requires many years and is also relatively fast. However, by using a polymer blending process that is reasonably inexpensive to use, it is often possible to reduce commercialization time by perhaps two to three places [1, 2]Polymer nanocomposites are new types of hybrid materials obtained by homogeneously dispersing at least one-dimensional nano-sized inorganic particles in a polymer matrix. Polymeric nanocomposites are prepared to enhance the performance properties of polymer materials [3].Their natural regularities reinforced with inorganic dopants of polymer nanocomposites have made them indispensable for 50 years. With their developed properties, polymer nanocomposites can be used in various applications such as biomedical materials, functional textile fibers, membrane manufactures, drugs, and catalysts electrons [4, 5].What makes polymer nanocomposites demandable is the flexibility of the polymer matrix, lower costs, and synergic interaction between matrix and nanoparticles that depends on the electrical, chemical, mechanical, and catalytic properties of nanoparticles [6].

The first study on the PVC/PMMA blend was carried out to examine the effect of the tacticity of PMMA on interaction with PVC [7].Hong et al. (2000) [8] examined the effect of solvent on the miscibility of PVC/PMMA depending on the Huggins’ constant. In this study, while they found the Huggins’ k’ constant of THF for PVC to be 0.6, the same constant was found for PMMA to be 0.87. The Huggins’ k’ constant measured for PMMA showed that THF between the range 0.8 < k < 1.3 is a weak solvent for PMMA.Saeed and Khan [9] found PMMA/PVC (10% by weight PMMA/90% by weight PVC) α (alpha) and (20% by weight PMMA/80% by weight PVC) β (beta)) mixtures and functionalized multiwalled carbon nanotubes. (F-MWNTs) filled alpha and beta nanocomposites were prepared by the solution casting technique. They found that when the amount of F-WMNTs increased in alpha and beta mixtures, the mechanical properties of alpha and beta gradually decreased.

The percolation theorem can be applied to explain the electrically conductive behavior of composites composed of conductive fillers and insulating matrices. The lowest concentration of dopant that makes the nanocomposite conductive is called the percolation threshold [10]. The percolation theory can be expressed by the following formula:

$$\:\sigma\:\:\approx\:\:{\sigma\:}_{0}\:(P\:-{P}_{c}\:)t$$

In Eq. (1), σ₀ is a constant. P is the CNT weight fraction, Pc is the CNT weight fraction corresponding to the percolation threshold, and t is a fore-exponential factor that depends on the conductivity, contact resistance, and network topology of the fillers [11].

PMMA with an average molecular weight of 15,000, low molecular weight PVC, 6–13 nm × 2.5–20 µm, > 98% CNTs, and > 99.9% purity tetrahydrofuran (THF) used in this study were obtained from Sigma-Aldrich. Furthermore, Dathan MS-MP8 was used as a magnetic stirrer, and Lab Companion Ultrasonic Cleaner was used as an ultrasonic bath.

The method is based on Yanmaz [12]. The solid mixing of 1-g PVC and PMMA was prepared in a 50:50% ratio (500 mg PVC/500 mg PMMA). CNTs were weighed as 0.1, 0.5, and 1% of the total polymer mixture. The polymer mixture was dissolved in THF, and then the dispersions of CNTs with THF were added into 30-mL polymer solutions. The new dispersion was first homogenized in an ultrasonic bath for two hours and then on the magnetic stirrer for one hour. Finally, homogeneous dispersions were carefully poured into petri dishes. Nanocomposite films were obtained after waiting 24 hours at room temperature.

The polymer blend was coded as PVC50 because polymer blends were prepared with 50% of PVC. However, the nanocomposite was named according to the percentage of CNT doping as PVC50-0, PVC50-0.1, PVC50-0.5, and PVC50-1.

Sigma 300 FESEM was used in SEM viewing. Rigaku Ultima IV X-Ray was used in XRD ( X Ray Diffractometer) analysis. Hitachi STA 7300 TGA/DTA was used in TGA (thermogravimetric analysis). Perkin Elmer Diamond was used in the DSC (Differential Scanning Calorimeter) analysis. Finally, the Keithley Model 6517A Electrometer was used in electrical conductivity measurements.

Experimental

Figure 2. PVC40-0.1 SEM images a: K X50000, b: K X 200000

Figure 4. PVC40-1 SEM images a: K X50000, b: K X 200000

Table 1

PVC40 (0–1) Series XRD results

	2 θ (⁰)	Crystallinity %
PVC40-0	16.18 23.54 39.74	13.69
PVC40-0.1	16.68 23.56 38.74	14.66
PVC40-0.5	17 25.18 40.44	13.92
PVC40-1	16.78 23.28 38.92	15.24
Average Crystallinity %		13.69

Table 2

PVC40 (0–1) Series Tg Values
Sample Code	Tg (°C)
PVC40-0	64.05
PVC40-0.1	66.90
PVC40-0.5	66.21
PVC40-1	64.06

Table 3

PVC40 (0–1) Series TGA values

Sample Code	T₁ (°C)	Weight Loss %	T₂ (°C)	Weight Loss %	T₃ (°C)	Weight Loss %	T_f (°C)	Maximum Weight Loss %
PVC40-0	194.11	5.26	349.42	36.16	442.95	88.92	473.70	92.61
PVC40-0.1	193.39	4.86	348.72	36.98	442.19	86.78	473.01	90.61
PVC40-0.5	194.09	5.02	349.43	36.07	442.28	80.80	473.62	90.15
PVC40-1	193.42	4.26	348.60	33.99	442.29	87.97	473.01	84.32

Table 4

PVC40 (0–1) Series DTG (Thermal degradation/minute) results
Sample Code	Td₁(°C)	Weight/Min.	Td₂ (°C)	Weight/Min.
PVC40-0	282.95	258.95	398.82	514.19
PVC40-0.1	308.75	119.78	399.24	248.86
PVC40-0.5	303.57	102.21	399.21	238.30
PVC40-1	297.14	79.31	402.84	200.41

Table 5

PVC40 (0–1) Series electrical conductivity results.
CNT (%)	PVC40 σ (S/cm)
0	7.69 × 10^− 16
0.1	1.50 × 10^− 15
0.5	4.5 × 10^− 13
1	1.27 × 10^− 7

Physical fragility was observed in all the samples. However, increasing the amount of CNT slightly reduced the fragility. This observation can be explained by a good interaction between CNT and polymer matrix [13]. Additionally, we could explain this phenomenon according to [14].

According to its ratio, it has been observed that PMMA becomes more visible in the polymer blend in the SEM images (shown in Fig. 1a, b, c). It can be thought that dipole-dipole interactions occurring in the neighbor chains via Cl-Cl bounding were fettered by the present PMMA molecules, as supported by [15]. Other images showed that CNTs dispersed well enough and interacted well with the polymer matrix.

The amorphous character of the nanocomposite was exposed by the XRD analysis (shown in Fig. 5). This observation is compatible with [16] and [17]. Crystallinity decreased with 0.1 and 0.5% of CNT; however, it was observed that crystallinity increased again with 1% of CNT (shown in Table 1). Because CNTs in this study were not functionalized with any chemical group like -COOH or -OH, this situation between CNTs and polymer matrix without any chemical binding can be explained with electrostatic interaction and Van der Waals forces or micromechanical locking up [18]. A similar effect of nanomaterial in crystallinity was observed by Althobiti et al. [19]. In a similar study, the researchers prepared a PVC/PMMA/TiO₂ nanocomposite and found that the dopant reduced the crystallinity of the samples [20].

A curve with three weight loss stages in TGA occurred (shown in Fig. 6, Table 2). The first loss was terminated at 194°C. The second level of degradation can be explained with a dehydrochlorination that looks very similar to [21]. In our study, the second degradation level started atre about 220°C and reached a maximum temperature of approximately 470°C. These results look remarkably similar to those of other studies on polymer blends, including the chlorinate group such as PVC [22].

Despite the fragility of the nanocomposite, there is only one Tg value and endothermic curve (shown in Fig. 7, Table 3). This is compatible with the criteria of miscibility presented in [23]. However, there is no correlation between Tg values and CNT amounts.

DTG results showed that CNT doping reduced the rate of weight loss (shown in Fig. 8, Table 4). In this situation, it can be supposed that there is a good interaction between CNTs and polymer blend. Due to good interaction, CNTs can help preserve the integrity of nanocomposites. The curves and values of the nanocomposite with CNT confirm this supposition. These data were compatible and explicable with [9] and [24].

Electrical conductivity reached 1.2 × 10^− 7 S/cm with only 1% of CNT. Till this amount, any increase was not measured in the electrical conductivity. In this situation, according to Sah and Gupta [25], it can be thought that solvent-polymer interaction could make the percolation weaken. In a study with various polymer/MWCNT nanocomposites, Zare et al. [26] found the biggest L_c ( Interfacial conductivity) in the PVC/MWCNT nanocomposite. Our study found a conductivity curve highly similar to their findings. This showed that at the near concentration of CNTs, conductivity and percolation in polymer nanocomposite can be affected by the concentration of the polymeric dispersion phase. According to the results of this study, it can be said that the PVC/PMMA polymer blend has > 50 PMMA and cannot make any positive contribution to physical strength and electrical conductivity.

In this study, we observed that our composite could be useful in certain circumstances. This nanocomposite could be used as a flexible and convenient material in electrical/electronic applications if it can be adjusted in an optimal polymer ratio. The conductivity curve of the nanocomposite seems promising for further research on the relationship between the ratio of polymers and CNT amounts. This study can encourage other studies on common industrial polymer blends to develop their proper new forms.

Acknowledgments

This study was supported by the YYU Scientific Research Projects Coordination Unit as part of the project numbered FDK-2020-8776.

Author contributions:

There are contributions of authors in this article that derived from PhD as below:

Asc. Prof. Mustafa Hamdi KARAGÖZ was contibuted to Conceptial, supervision and advisement. PhD. Afşar ÇELİK was contributed to Methodology, experimental design, analyses, carrying out measurements, manuscript composition.

Conflicts of interest or competing interests:

The authors declare that there is no conflict of interest or competing interest in this article.

Data and code availability

Data will be made available on request.

Ethical approval:

There is no ethical approval needed for this article.

J.J. Jr. Scobbo, L.A. Goettler, Polymer Blends Handbook, 2nd edn., ed. by L.A. Utracki (Kluwer Academic, Netherland, 2003)
S. Thomas, P. GrohensY, Jyotishkumar, Characterization of Polymer Blends: Miscibility, Morphology, and Interfaces (Wiley-VCH Verlag GmbH & Co. Weinheim, 2015)
E.M. Masoud, L. Liu, B. Peng, Synthesis, Characterization, and Applications of Polymer Nanocomposites. J. Nanomater. (2020). https://doi.org/10.1155/2020/5439136
S. İçli, Polimerik Kompozitler: Geleceğin Teknolojileri. I. Polimerik Kompozitler Sempozyumu ve Sergisi (İzmir, Türkiye, 2006)
J. Luan, S. Wang, Z. Hu, L. Zhang, Synthesis Techniques, Properties and Applications of Polymer Nanocomposites. Curr. Org. Synth. https//. (2012). 10.2174/157017912798889161
M. Muhammed Shameem, S.M. Sasikanth, R. Annamalai, R. Ganapathi Raman, (2021) A brief review on polymer nanocomposites and its applications. Materials Today: Proceedings. https://doi.org/10.1016/j.matpr.2020.11.254
J.W. Schurer, de A. Boer, G. Challa, Influence of tacticity of poly(methyl methacrylate) on the compatibility with poly(vinyl chloride). Polymer. 16, 201–204 (1975)
P.-D. Hong, H.-T. Huang, C.-M. Chou, Study of the solvent effect on miscibility between poly(vinyl chloride) and poly(methyl methacrylate) in the solution state-viscometric measurements. Polym. Int. 49(4), 407–411 (2000)
K. Saeed, N. Khan, Preparation, morphologies and properties of multiwalled carbon nanotubes-filled PMMA/PVC blends. J. Chem. Soc. Pakistan. 37(2), 284–289 (2015)
D. Ponnamma, N. Ninan, S. Thomas, Applications of Nanomaterials, ed. by S.M. Bhagyaraj, S.O. Oluwafemi, N. Kalarikkal, S. Thomas (Woodhead Publishing, UK, 2018)
M. Fogel, P. Parlevliet, M. Geistbeck, P. Olivier, E.D. Dantras, Thermal, rheological and electrical analysis of MWCNTs/epoxy matrices. Compos. Sci. Technol. 110, 118–125 (2015)
E. Yanmaz, (2018) Vinil Grubu İçeren Bazı Polimer / Modifiye Tek Duvarlı Karbon Nanotüp Nanokompozitlerinin Sentezi ve Karakterizasyonu.(PhD Thesis) BÜ, Fen Bilimleri Enstitüsü, Balıkesir, TÜRKİYE
S.M. Luna, G. Filippone, Effects of nanoparticles on the morphology of immiscible polymer blends – Challenges and opportunities. Eur. Polym. J. 79, 198–218 (2016)
M. Hisham, C.M. Shebeeb, C. Dileep, L. Jacob, H. Butt, Additive manufacturing of carbon nanocomposites for structural applications. J. Mater. Res. Technol. (2024). https://doi.org/10.1016/j.jmrt.2024.01.049
R. Chakrabarti, M. Das, D. Chakraborty, Physical, mechanical, and thermal properties of PVC/PMMA blends in relation to their morphologies. J. Appl. Polym. Sci. 93(6), 2721–2730 (2004)
V.S.A. Sangawar, A.N. Moharil, Study of electrical, thermal and optical behavior of polypyrrole filled PVC:PMMA thin film thermoelectrets. Chem. Sci. Trans. 1(2), 447–455 (2012)
S. El-Gamal, M. Elsayed, Synthesis, structural, thermal, mechanical, and nano-scale free volume properties of novel PbO/PVC/PMMA nanocomposites. Polymer. 206(29), 1–17 (2020)
S.K. Swain, I. Jena, Polymer/carbon nanotube nanocomposites: A novel material. Asian J. Chem. 22(1), 1–15 (2010)
R. Althobiti, M. Morsi, E. Alzahrani, A. Al-Muntaser, Enhancing the performance of PVC/PMMA polymer blend through hybrid nanofiller of TiO2 NPs/GNPs for capacitive energy storage applications. Ceram. Int. (2024). 10.1016/j.ceramint.2024.03.001
A. Al-Muntaser, H.M. Abo-Dief, A.E. Tarabiah, E. Alzahrani, H.A. Alsalmah, Z.M. Alharbi, R.A. Pashameah, A. Saeed, Incorporated TiO2 nanoparticles into PVC/PMMA polymer blend for enhancing the optical and electrical/dielectric properties: Hybrid nanocomposite films for flexible optoelectronic devices. Polym. Eng. Sci. (2023). https://doi.org/10.1002/pen.26476
A.F.A. Naim, H. Al Fannakh, S. Arafat, S.S. Ibrahim, Characterization of PVC/MWCNTs Nanocomposite: Solvent blend. Sci. Eng. Compos. Mater. 27(1), 55–64 (2020)
C. Evangelia, T. Vouvoudi, Aristea, S. Rousi, Dimitris, Achilias, Effect of the catalyst type on pyrolysis products distribution of polymer blends simulating plastics contained in waste electric and electronic equipment. Sustain. Chem. Pharm. (2023). https://doi.org/10.1016/j.scp.2023.101145
M. Ferriol, A. Gentilhomme, M. Cochez, N. Oget, J.L. Mieloszynski, Thermal degradation of poly(methyl methacrylate) (PMMA): modelling of DTG and TG curves. Polym. Degrad. Stab. 79(2), 271–281 (2003)
M. Dixit, V. Mathur, S. Gupta, M. Baboo, K. Sharma, N.S. Saxena, Investigation of miscibility and mechanical properties of PMMA/PVC blends. J. Optoelectron. Adv. Mater. Rapid Commun. 3(10), 1099–1105 (2009)
G.K. Sah, A.K. Gupta, Miscibility studies of PVC/PMMA blends in tetrahydrofuran by viscosity, density, refractive index and ultrasonic velocity method. Nanosyst: Phys. Chem. Math. 4(2), 288–293 (2013)
Y. Zare, K.Y. Rhee, S.J. Park, Nanomaterials, https://doi.org/10.3390/nano12142383

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Spectroscopic, Thermal and Electrical Properties of CNT Added PVC/PMMA Blends

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