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Abstract

Polyvinylidene fluoride (PVDF) is one of the established thermoplastics with inherent piezoelectric characteristics. In the past two decades, a lot of work has been reported on the use of virgin Polyvinylidene fluoride thermoplastics for sensing applications. But hitherto little has been reported on 3D printing of secondary (2°) recycled Polyvinylidene fluoride as a smart energy storage device (ESD). This work is focused on exploring the possibilities for 3D printing of smart energy storage device comprising of Polyvinylidene fluoride having (melt flow index (MFI) 30g/(10 min) as per ASTM D 1238) reinforced with MnO₂, graphite, ZnCl_2, and N $H_{4}$ Cl in different weight proportions to form a feedstock filament for fused deposition modeling (FDM) in the first stage. The MFI of Polyvinylidene fluoride composites reinforced with MnO₂, graphite, ZnCl_2, and N $H_{4}$ Cl (34.095, 8.480, 42.982, 11.807g/(10 min) respectively) was ascertained for possible 3D printing on FDM. The results suggest that even with an acceptable MFI of prepared 2° recycled Polyvinylidene fluoride, the same was not printable. Further for possible 3D printing on FDM, low-density polyethylene (LDPE) was blended in a Polyvinylidene fluoride matrix, and successful 3D printing-based energy storage device was prepared in the second stage. The study also highlights the mechanical, and morphological properties of Polyvinylidene fluoride composites have been improved after processing with a twin-screw extruder (TSE) by using different input parameters (screw temperature (T), screw speed (S), and load (L)). Overall, the study suggests that the proportion of LDPE, MnO₂, graphite, ZnCl_2, and N $H_{4}$ Cl has a significant effect on the rheological, mechanical, and morphological properties. The results have been supported with scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and Fourier-transformed infrared spectroscopy (FTIR) analysis.

Keywords

Polyvinylidene fluoride melt flow index twin-screw extruder electrical properties composite matrix

Introduction

Additive manufacturing (AM)/3D printing is being widely used for creating a 3D object through a digital mode involving successive layers of material.¹ Various slicing methods have been adopted by researchers to overcome the issue of build time^2,3 and surface quality⁴ in 3D printing.⁵ In today’s scenario, various smart materials such as shape memory and piezoelectric materials have gained the limelight due to their unique potential to retain their desired shape when activated by external stimuli.^6–8 Piezoelectric materials also have the unique ability to produce voltage under some external load which increases their effectiveness in energy harvesting and structural health monitoring applications.^9,10 Piezoelectric materials such as lead zirconate titanate and ZnO have been extensively utilized by researchers for transducer applications.¹¹ The accumulation of energy in any particular form is one of the better alternatives to cope with the demand and supply of energy. One such method of energy storage in the form of a dry cell has been in commercial practice for a long.¹²

In the past two decades, extensive work has been reported on recycling thermoplastics by reinforcing them with metallic powders.¹² Further preparation of feedstock filament of different reinforced materials using a 3D printer based on FDM has been reported by several researchers.^13,14 Two different 3D printing techniques namely inkjet and direct writing have been widely adopted by the researchers for the electro-chemical ESD.¹⁵ The literature emphasizes reinforcement of different chemicals into thermoplastics made them conductive and hence possess better mechanical, thermal, and electrical properties.¹⁶ Researchers have cited the applications of 3D printing for the fabrication of devices namely sensors, conductors,¹⁷ feedstock filament based on FDM,¹⁸ wear-resisting materials,¹⁹ the stretchable electrode for flexible supercapacitors,²⁰ 4D applications for PVDF reinforced with graphene and barium titanate,²¹ pressure sensing using piezo-resistive materials reinforced with carbon nanotubes,²² heritage structures.²³ A comparative analysis of both mechanically, as well as chemically blended composites of PVDF matrix reinforced with graphene and barium titanate for 3D printing applications, has been reported by the researchers.²⁴ The main characteristic of dry cells is the conversion of chemical energy into electrical energy and literature has been reported on the types and construction of the dry cell.²⁵ Usually, cells are categorized into primary (non-rechargeable) and secondary (rechargeable). The construction of a dry cell consists of a graphite rod in the center acting as a cathode. The graphite rod is surrounded by Mn $O_{2}$ all around it. Two different electrolytes N $H_{4}$ Cl and Zn ${Cl}_{2}$ are used for the transfer of ions and the whole setup is enclosed in a zinc casing which serves as an anode.²⁵ The literature review reveals that in the past two decades, a lot of work has been reported on 3D printing^26–29 and the use of virgin PVDF thermoplastics³⁰ for sensing applications. Researchers have also explored the fabrication of a flame retardant and recyclable ESD using MnO₂, graphite, ZnCl_2, and N $H_{4}$ Cl salt in the matrix of acrylonitrile butadiene styrene (ABS).³¹ Studies have also been reported on the formation of β phase in PVDF films due to the application of mechanical load as the stimuli which is of prime importance in charge storing applications.³² Researchers have also explored the 4D applications of PVDF reinforced with graphene and barium titanate.³³ Studies have also been reported on the piezoelectric and dielectric properties of PVDF reinforced with barium titanate nanocomposites and the results have been compared with solvent-based nanocomposites.³⁴ But hitherto little has been reported on 3D printing of 2° recycled PVDF as a smart ESD. This study is focused on exploring the charge-storing capability of 3D printed PVDF-based ESD through its voltage (V)- current (I) characteristics which may help to determine the life of a dry cell. Furthermore, prepared PVDF composite-based smart ESD may be used for online condition monitoring and self-charging capabilities.

Experimentation

In stage 1, primary recycled PVDF having MFI 30g/(10 min) as per ASTM D 1238 was used as per previously reported studies.^35,36 For the preparation of feedstock filament from PVDF, the TSE setup (Make-Thermo-Fisher Scientific Haake miniCTW, Germany) was used. Three input parameters namely: T, S, and L were selected (based on a pilot study), and the design of the experiment (DOE) according to Taguchi L₉ orthogonal array (OA) was used for further experimentation. The 09 sets of extruded wire filaments (with three repetitions) as per Table 1 were tested on the universal tensile testing machine (UTM) (Make-Shanta Engineering, Pune, Maharashtra, India) to ascertain the mechanical properties. The filament with higher Young’s modulus (E) was selected to ensure printability via an open-source 3D printer (Table 1, S.No.4).

Table 1.

Observations for mechanical properties of PVDF (with three repetitions).

S. No.	T (°C)	S (rpm)	L (kg)	PL (N)	PE (mm)	BL (N)	BE (mm)	PS (MPa)	BS (MPa)	E MPa
1	210	100	5	2.9	21.84	2.61	36.33	0.59	0.53	1.08
2	210	110	8	2.9	47.25	2.61	50.61	0.59	0.53	0.49
3	210	120	11	1.9	9.03	1.71	12.18	0.39	0.35	1.72
4	220	100	8	0.4	0.84	0.36	37.59	0.08	0.07	3.80
5	220	110	11	4.9	161.49	4.41	166.32	1.00	0.9	0.24
6	220	120	5	3.9	175.35	3.51	294.21	0.79	0.72	0.18
7	230	100	11	3.9	180.81	3.51	215.46	0.79	0.72	0.17
8	230	110	5	3.8	178.23	3.46	200.67	0.76	0.69	0.17
9	230	120	8	3.7	170.56	3.39	190.56	0.67	0.65	0.15

Note: Peak load: PL, Peak elongation: PE, Break load: BL, Break elongation: BE, Strength at peak PS, Strength at break: BS.

For the fabrication of ESD, Mn

O_{2}

, graphite, Zn

{Cl}_{2}

and N

H_{4}

Cl was reinforced into the PVDF matrix as per Table 2. Based on MFI values (Table 2) the weight (%) of Mn

O_{2}

, graphite, Zn

{Cl}_{2}

and N

H_{4}

Cl was ascertained. The ascertained weight (%) of Mn

O_{2}

reinforced into the PVDF matrix were then treated on TSE for extruding the feedstock filament based on DOE (Table 3). The extruded 09 sets of wire filaments were tested on UTM to obtain the mechanical properties. As per Table 3 (S.No.4), the filament with better E was selected to ensure printability on the 3D printer. Similarly, the experimentation was performed for the other chemicals reinforced into the PVDF matrix. The applied methodology for stage 1 is shown in Figure 1.

Table 2.

MFI values (average of three observations) for different compositions/proportions.

Ratio of PVDF + chemical/salt (%)	MFI of Mn $O_{2}$ g/(10 min)	MFI of graphite g/(10 min)	MFI of Zn ${Cl}_{2}$ g/(10 min)	MFI of N $H_{4}$ Cl g/(10 min)
90 + 10	13.450	27.078	30.510	24.468
70 + 30	51.500	18.990	32.266	11.807
50 + 50	34.095	8.480	42.982	Chocking
30 + 70	Chocking	Chocking	Chocking	–

Note: The highest possible composition/proportion of chemical was selected with the possibility of 3D printing.

Table 3.

Observations for PVDF + 50% Mn $O_{2}$ (with three repetitions).

S. No.	T (°C)	S (rpm)	L (kg)	PL (N)	PE (mm)	BL (N)	BE (mm)	PS (MPa)	BS (MPa)	E MPa
1	170	100	5	1.4	5.25	1.26	13.65	0.29	0.26	2.20
2	170	110	8	2.9	43.47	2.61	64.26	0.59	0.53	0.54
3	170	120	11	1.4	4.41	1.26	11.13	0.29	0.26	2.63
4	180	100	8	0.4	0.42	0.36	6.3	0.08	0.07	7.61
5	180	110	11	0.4	36.63	0.36	37.59	0.08	0.07	0.08
6	180	120	5	1.9	13.86	1.71	17.01	0.39	0.35	1.12
7	190	100	11	2.4	8.61	2.16	14.07	0.49	0.44	2.27
8	190	110	5	1.4	3.36	1.26	6.93	0.29	0.26	3.45
9	190	120	8	1.9	17.01	1.71	25.62	0.39	0.35	0.91

Figure 1.

Flow diagram for experimental methodology (stage 1).

It may be noted that a significant dip in processing temperature conditions for PVDF (210°C–230°C, Table 1) and PVDF matrix (170°C–190°C Table 3) was selected. Since the melting range of PVDF lies at 210°C–230°C, the same was selected for processing PVDF (Table 1). The addition of MnO₂ resulted in lowering the melting range of the composite matrix therefore the processing condition of 170°C–190°C was selected. This was based upon uniform diameter wire (φ 1.75 ± 0.10 mm) preparation on TSE, over burning of samples at a temperature higher than 190°C (visual observations).

Based upon Figure 1, Tables 1 and 3 samples at S.No. 4 (of PVDF, PVDF-MnO₂) were explored for 3D printing on FDM at different process parameters (infill density, print bed/nozzle temperature, infill patterns, raster angle, infill speed, etc.). However unsuccessful printing was observed. A similar trend was noticed for the 3D printing of PVDF with graphite, ZnCl₂, and NH₄Cl.

In stage 2, for successful printing of the PVDF matrix, 40% LDPE (by weight.) was blended. This proportion of LDPE was selected based upon two factors: (i) availability of recyclable LDPE with a higher E value, and (ii) uniform size wire formation (visual observation). The corresponding MFI values (with three repetitions) are shown in Table 4.

Table 4.

MFI values for different salts reinforced into PVDF matrix (60%PVDF+40% LDPE).

Ratio of PVDF + chemical/salt (%)	MFI of Mn $O_{2}$ g/(10 min)	MFI of graphite g/(10 min)	MFI of Zn ${Cl}_{2}$ g/(10 min)	MFI of N $H_{4}$ Cl g/(10 min)
90 + 10	19.230	15.338	19.064	21.485
70 + 30	28.887	7.782	34.735	12.544
50 + 50	11.970	3.616	41.921	5.610

Note: These additives (MnO₂, graphite, ZnCl₂, and NH₄Cl) were selected based on their use in conventional dry cells. The compositions of selected salts are responsible for converting chemical energy into electrical energy.

Based upon Tables 2 and 4 it has been ascertained that significant variation in MFI occurs with a blending of LDPE and as a thumb rule higher MFI leads to the fabrication of thin sections and vice versa. Further, by using the PVDF matrix (60% PVDF+40% LDPE) + 50% MnO₂, feedstock filaments were prepared using TSE, and their corresponding mechanical properties are shown in Table 5.

Table 5.

Observations for PVDF matrix (60% PVDF+40% LDPE) + 50% MnO₂ (with three repetitions).

S. No.	T (°C)	S (rpm)	L (kg)	PL (N)	PE (mm)	BL (N)	BE (mm)	PS (MPa)	BS (MPa)	E MPa
1	135	70	5	10.7	3.78	9.63	4.20	2.18	1.96	23.06
2	135	75	8	8.8	9.66	7.92	9.87	1.79	1.61	7.41
3	135	80	11	6.3	6.72	5.67	7.35	1.28	1.16	7.61
4	140	70	8	2.9	0.84	2.61	28.35	0.59	0.53	28.09
5	140	75	11	9.8	2.73	8.82	2.94	2.00	1.80	29.30
6	140	80	5	44.6	7.56	40.14	9.03	9.09	8.18	48.09
7	145	70	11	14.2	4.41	12.78	5.67	2.89	2.6	26.21
8	145	75	5	18.1	2.1	16.29	2.31	3.69	3.32	70.28
9	145	80	8	7.8	3.99	7.02	5.46	1.59	1.43	15.93

Note: The range/levels of input parameters: T, S, and L are based upon pilot experimentation for getting uniform diameter wire.

Based upon Table 5, S.No.8 with higher E was selected for 3D printing on FDM, and successful printing as substrate was achieved at 55°C bed temperature, 160°C nozzle temperature, raster angle 0°, with rectilinear infill pattern. Similarly, successful printing of PVDF matrix (60% PVDF+40% LDPE) + 50% Graphite/NH₄Cl/ZnCl₂ was achieved (Figure 2).

Figure 2.

3D printing of PVDF matrix (60% PVDF+40% LDPE) + 50% Graphite/MnO₂/NH₄Cl/ZnCl₂ with two nozzle 3D printer. Note: The dual-nozzle system (open-source commercial setup Prusa 3D printer, with build volume 360 × 360 × 360 mm) was used to feed different feedstock filaments.

Results and discussion

To ascertain the reason for the unsuccessful printing of samples with the highest E (based upon Tables 1 and 3) and successful printing (based upon Table 5), signal to noise (SN) ratio was calculated (Table 6) for the ‘maximum the better’ type case. Table 7 shows an analysis of variance (ANOVA) based on Table 6 and corresponding mean effect plots are shown in Figure 3.

Table 6.

SN ratios for E.

S. No.	Based on Table 1	Based on Table 3	Based on Table 5
1	0.673187	6.885974	27.26049
2	−6.0298	−5.30555	17.39872
3	4.748737	8.400388	17.63801
4	11.61741	17.63801	28.97265
5	−12.1217	−21.1737	29.33855
6	−14.8844	1.027227	33.64204
7	−15.1507	7.145058	28.37038
8	−15.3621	10.76237	36.93734
9	−16.0748	-0.75159	24.04968

Table 7.

ANOVA for SN ratios (as per Table 6).

For SN ratios of E as per Table 1
Parameters	Degree of freedom	Sequential sum of squares	Adjusted sum of squares	Adjusted mean of squares	Fisher’s (F) value	Probability (P)
T	2	367.33	367.33	183.67	1.46	0.406
S	2	170.91	170.91	85.46	0.68	0.595
L	2	62.09	62.09	31.05	0.25	0.802
Error	2	251.21	251.21	125.6
Total	8	851.55
For SN ratios of E as per Table 3
T	2	66.02	66.02	33.01	0.14	0.875
S	2	373.35	373.35	187.17	0.81	0.552
L	2	104.13	104.13	52.06	0.23	0.816
Error	2	462.17	462.17	231.09
Total	8	1006.67
For SN ratios of E as per Table 5
T	2	179.830	179.830	89.915	59.83	0.016
S	2	17.389	17.389	8.695	5.79	0.147
L	2	141.443	141.443	71.222	47.39	0.021
Error	2	3.006	3.006	1.503
Total	8	342.668

Figure 3.

Mean effect plot of SN ratios for larger the better type case (a) as per Table 1, (b) as per Table 3, and (c) as per Table 5.

Based upon Table 7, it has been ascertained that no TSE parameter was found significant at a 95% confidence level for E in the case of PVDF and PVDF + 50% Mn $O_{2}$ as no parameter was observed with a p-value < .05. But for the PVDF matrix (60%PVDF+40% LDPE) + 50% MnO₂, TSE parameters T and L were observed as significant. Also, the error contribution is very less i.e., < 1%. The best settings for E were observed as T 140°C, S 70 r/min, and L 5 kg. The probable reason for TSE insignificant input parameters for E in the case of PVDF and PVDF + 50% Mn $O_{2}$ maybe the piezoelectric nature of the material. The PVDF at room temperature without the stimuli (voltage, mechanical load) exists in α-phase. But once mechanical load is applied the PVDF shifts to β-phase which may overall affect the E and other mechanical properties. On the other hand, once 40%LDPE was put into the PVDF matrix, this may have resulted in difficulties for conversion in β-phase.

For further analysis, the extruded filaments of recycled PVDF and PVDF reinforced with Mn $O_{2}$ having best and worst mechanical properties (as per Tables 1 and 3) were exposed to microscopic examination (Jeol Jsm-6510LV SEM (Japan) at ×100). Metallurgical image analysis software (MIAS) was used for the porosity analysis as per ASTM B276. The porosity%, 3D rendered image, surface roughness (Ra), amplitude distribution function (ADF) representing the probability of getting high peak as surface characteristics, and peak count (PC) of best and worst samples (based upon E) for recycled PVDF and PVDF reinforced with Mn $O_{2}$ are shown in Figures 4 and 5 respectively.

Figure 4.

Recycled PVDF with highest E (as per Table 1, S.No.4) (a) Porosity %, (b) 3D rendered image, (c) Ra profile, (d) ADF, (e) PC, Recycled PVDF with lowest E (as per Table 1, S.No.9) (f) Porosity %, (g) 3D rendered image, (h) Ra profile, (i) ADF, (j) PC.

Figure 5.

Recycled PVDF+50%MnO₂ with highest E (as per Table 3, S.No.4) (a) Porosity %, (b) 3D rendered image, (c) Ra profile, (d) ADF, (e) PC, Recycled PVDF +50%MnO₂ with lowest E (as per Table 3, S.No.5) (f) Porosity %, (g) 3D rendered image, (h) Ra profile, (i) ADF, (j) PC.

As observed from Figure 4 porosity% for a sample with the highest E is 3.74% in comparison to a sample with the lowest E (25.91%) for recycled PVDF. Also, the Ra for the best sample (9.846µm) is less in comparison to the worst sample (14.56 µm). Further ADF for a sample with the lowest E is distorted and the PC value is relatively higher than the sample with the highest E. The Ra value is in correlation with the ADF since the area under the curve for the worst sample is more in comparison to the area under the curve for the best sample which indicates their higher probability and high roughness value. Similarly, the porosity of PVDF-reinforced MnO₂ for a sample with the highest E is 19.02%, lower than a sample with the lowest E (34.84%) (Figure 5). A similar trend was noticed for other surface properties (ADF and PC). Figure 6 shows EDS plots for samples of PVDF and PVDF+MnO₂ with the highest E (for confirming the presence of Mn in a selected zone).

Figure 6.

EDS plots for Recycled PVDF with highest E (as per Table 3, S.No.4) (a), Recycled PVDF +50%MnO₂ with highest E (as per Table 3, S.No.4) (b).

For further analysis, the absorbance spectrum (Figure 7) was obtained from FTIR of PVDF and PVDF-MnO₂ composite having the highest and lowest E (as per Tables 1 and 3). Based upon Table 1, the recycled PVDF sample at S.No. 4, highlights the presence of -CH₂- group at 2900cm⁻¹ wavenumber (WN), and C-C bonds were observed at 2865 WN (Figure 7(a)). Similar observations were noticed for a sample at S.No. 9 (Figure 7(b)). The reduction in E for sample 9 may be because of an increase in porosity % (Figure 4). As observed from Figure 7(c) and (d) the peaks were obtained at 825-840 WN for C-F molecules and 750-1029 WN for C=O in PVDF-MnO₂ composite samples. The formation of such bonding structures resulted in an improved modulus of toughness, E, that contributed to increased conductivity and piezoelectric properties of PVDF by inducing the β phase in the composite.

Figure 7.

Absorbance spectrum of PVDF and PVDF-MnO₂ composite samples. (a) PVDF Sample 4. (b) PVDF Sample 9. (c) PVDF-MnO₂ Sample 4. (d) PVDF-MnO₂ Sample 5.

Further V-I and V-resistance (R) properties of recycled PVDF and PVDF matrix reinforced with Mn

O_{2}

were calculated using the Source meter unit (Make-Keithley, 2461). It was observed that at 1.5V the value of resistance is 80Ω when no chemical was reinforced into the recycled PVDF but at the same voltage the value of resistance drops to 58Ω when recycled PVDF was reinforced with Mn

O_{2}

The drop in resistance signifies that resistivity decreases and hence electrical conductivity increases which signifies that the charge storing capacity increases due to reinforcement of Mn

O_{2}

into the PVDF matrix. This unique characteristic of the charge-storing capability of PVDF may be used to determine the life/health of ESD for online condition monitoring. Further, Table 8 shows the comparative analysis of observed properties for recycled PVDF, recycled PVDF + 50% Mn

O_{2}

and PVDF matrix (60%PVDF+40% LDPE) + 50% MnO₂.

Table 8.

Comparison of different properties for recycled PVDF, recycled PVDF + 50% Mn $O_{2}$ , and PVDF matrix (60%PVDF+40% LDPE) + 50% MnO₂.

Sample	Twin screw extruder settings as per Figure 3			E (MPa)	Resistance at 1.5 V (Ω)
Sample	T (ºC)	S (rpm)	L (kg)	E (MPa)	Resistance at 1.5 V (Ω)
Recycled PVDF	220	100	8	3.80	80.0
Recycled PVDF + 50% Mn $O_{2}$	180	100	8	7.61	58.0
PVDF matrix (60%PVDF+40% LDPE) + 50% MnO₂	145	75	5	70.28	57.4

The XRD of PVDF (Figure 8(a)) and 60%PVDF+40%LDPE+50% MnO₂ (Figure 8(b)) shows phases (α, β) and the peaks of crystallinity. It has been observed that due to the reinforcement of LDPE in the PVDF matrix, the mechanical properties and its printability were improved, but certainly, it has weakened the piezoelectric property. But even after reinforcement of LDPE in the PVDF matrix, the β phase still exists (observed at 2θ= 20.66282°) in line with the reported literature.³⁷ Further, the comparison of FTIR curves for PVDF (Figure 8(c)) and 60%PVDF+40%LDPE+50% MnO₂ (Figure 8(d)) shows the presence of MnO_2. It has been noted that the (C-F) stretch at wave number 550 indicates the presence of PVDF (in line with reported literature).³⁸ Since in the present study the recycled PVDF was used, the C-F bond was noted at 468.5878 wave number (Figure 8(c)). The presence of MnO₂ as an O-Mn-O group is shown in Figure 8(d).

Figure 8.

XRD of PVDF (a) 60%PVDF+40%LDPE+50% MnO₂ (b) FTIR of PVDF (c) 60%PVDF+40%LDPE+50% MnO₂ (d).

Figure 9 shows V-R and V-I curves for 50% (graphite/ZnCl₂/N $H_{4}$ Cl reinforced in PVDF (60%PVDF+40% LDPE) matrix. A significant change in resistance has been noticed from recycled PVDF, Recycled PVDF + 50% Mn $O_{2}$ and PVDF matrix (60%PVDF+40% LDPE) + 50% MnO₂ (Table 8), hence required a separate study to ascertain its effect on the β phase in PVDF. Also, this significant difference in resistance will affect the charge-carrying capacity of the PVDF matrix, and its dielectric constant, which may be further tuned to ascertain the health of a 3D printed ESD using the concept of microstrip patch antenna.^39,40

Figure 9.

V-R and V-I curves for 50% (graphite/ZnCl₂/N $H_{4}$ Cl reinforced in PVDF (60%PVDF+40% LDPE) matrix. (a), (b).

Conclusions

(1) This study shows that 50 wt%. of (Mn $O_{2}$ , graphite, Zn ${Cl}_{2}$ ) and 30 wt%. N $H_{4}$ Cl when reinforced with a PVDF matrix affects the MFI (selected based on required flow characteristics) (in comparison to recycled PVDF. This may help in plastic solid waste management as the proposed route can be adopted for the recycling of ESD.

(2) The obtained mechanical properties in the case of PVDF+MnO₂ (E = 7.61MPa) matrix are better than recycled PVDF (E=3.80MPa) (for the selected lot of material in the present study). The results suggest that concerning E, the best composite filament of PVDF matrix reinforced with 50 wt% of Mn $O_{2}$ is formed at T 190°C, S 100 rpm, and L 5kg which gives some dispersion of chemicals/salt in the PVDF matrix. Here no TSE parameter was found significant maybe because of the piezoelectric behavior of PVDF. The microphotographs of the PVDF matrix reinforced with Mn $O_{2}$ indicates the non-uniform dispersion of Mn $O_{2}$ .

(3) The V-I and V-R characteristics show that resistance gets reduced from 80Ω to 58Ω due to the reinforcement of Mn $O_{2}$ into PVDF matrix which indicates that electrical conductivity increases and hence the charge storing capacity is enhanced which is beneficial for the fabrication of ESD.

(4) The experimental results show that the composites prepared with PVDF matrix were not printable due to the elastic nature of PVDF (high strain for a selected lot of recycled PVDF), so to address the printability issue, an LDPE was reinforced into the PVDF matrix to improve its stiffness and hence printability. It was observed that on the addition of LDPE (40%) into the PVDF matrix its stiffness increased and a sample was easily printable. Based upon experimental observations it has been ascertained that chemicals/salts Mn $O_{2}$ , graphite, Zn ${Cl}_{2}$ and N $H_{4}$ Cl, when reinforced into PVDF and LDPE matrix, their mechanical properties such as peak strength and break strength, increase significantly. This improvement in the mechanical properties is useful for the 3D printing of ESD.

(5) The finally prepared PVDF composite may be used in sensing the time left for unused chemicals in the dry cell and a signal in the form of an electromagnetic wave may be generated (like the patch antenna, with changing values of conductivity, dissipation/loss factor, permittivity, etc. by the consumption of chemical/salt). Hence this may be useful as an industrial IoT-based solution for estimating the life of ESD.

Further investigations may be conducted to establish the performance of ESD in totality that is, comprising all different zones of PVDF+LDPE+MnO₂/NH₄Cl/ZnCl₂/graphite.

Footnotes

Acknowledgements

The authors are thankful to DST (Government of India) for financial support under the FIST project (File No. SR/FST/COLLEGE/2020/997).

Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Funding

The author(s) disclosed receipt of the following financial support for the research, authorship, and/or publication of this article: This work was supported by the Department of Science and Technology, Ministry of Science and Technology, India (SR/FST/COLLEGE/2020/997).

ORCID iD

Rupinder Singh

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On 3D printed polyvinylidene fluoride-based smart energy storage devices

Abstract

Keywords

Introduction

Experimentation

Results and discussion

Conclusions

Footnotes

Acknowledgements

Declaration of conflicting interests

Funding

ORCID iD

References