This study explores the influence of the molecular weight and phase composition of polyvinylidene fluoride (PVDF) precursors on the structural, mechanical, and magnetoelectric properties of PVDF/cobalt ferrite (PVDF/CFO) composites fabricated by fused deposition modeling (FDM). It was shown that the composite PVDF/CFO printed from a precursor with a lower molecular weight contains a higher content of the electroactive phase, which eventually leads to a higher magnitude of the magnetoelectric coefficient. The lower molecular weight is advantageous due to its reduced melting point which simplifies the printing process. Despite the higher magnitude of the Young’s modulus of the composite PVDF/CFO printed from low molecular weight PVDF, the filaments remain suitable for additive manufacturing. Overall, the results demonstrate that precursor selection is a key parameter for optimizing the functionality and printability of FDM-printed magnetoelectric composites.
KopylSSurmenevRSurmenevaM, et al.Magnetoelectric effect: principles and applications in biology and medicine– a review. Mater Today Bio2021; 12: 100149.
MakarovaLAIsaevDAOmelyanchikAS, et al.Multiferroic coupling of ferromagnetic and ferroelectric particles through elastic polymers. Polymers2022; 14: 153.
4.
OmelyanchikAAntipovaVGritsenkoC, et al.Boosting magnetoelectric effect in polymer-based nanocomposites. Nanomaterials2021; 11: 1154.
5.
StolbovOVIgnatovAARodionovaVV, et al.Modelling the effect of particle arrangement on the magnetoelectric response of a polymer multiferroic film. Soft Matter2023; 19: 4029–4040.
6.
MaityKGarainSHenkelK, et al.Self-powered human-health monitoring through aligned PVDF nanofibers interfaced skin-interactive piezoelectric sensor. ACS Appl Polym Mater2020; 2: 862–878.
7.
ZhangLLiSZhuZ, et al.Recent progress on structure manipulation of poly(vinylidene fluoride)-based ferroelectric polymers for enhanced piezoelectricity and applications. Adv Funct Mater2023; 33: 2301302.
8.
ChenGChenGPanL, et al.Electrospun flexible PVDF/GO piezoelectric pressure sensor for human joint monitoring. Diam Relat Mater2022; 129: 109358.
9.
CannasCFalquiAMusinuA, et al.CoFe2O4 nanocrystalline powders prepared by citrate-gel methods: synthesis, structure and magnetic properties. J Nanoparticle Res2006; 8: 255–267.
10.
MartinsPLasherasAGutierrezJ, et al.Optimizing piezoelectric and magnetoelectric responses on CoFe2O4/P(VDF-TrFE) nanocomposites. J Phys D Appl Phys2011; 44: 495303.
11.
StolbovOVRaikherYL. Magnetostrictive and magnetoactive effects in piezoelectric polymer composites. Nanomaterials2024; 14: 31.
12.
SobolevKKolesnikovaVOmelyanchikA, et al.Effect of piezoelectric BaTiO3 filler on mechanical and magnetoelectric properties of Zn0.25Co0.75Fe2O4/PVDF-TrFE composites. Polymers2022; 14: 4807.
13.
PullarRC. Hexagonal ferrites: a review of the synthesis, properties and applications of hexaferrite ceramics. Prog Mater Sci2012; 57(7): 1191–1334.
14.
SilvaFGDepeyrotJCamposAFC, et al.Structural and magnetic properties of spinel ferrite nanoparticles. J Nanosci Nanotechnol2019; 19: 4888–4902.
15.
CaiXLeiTSunD, et al.A critical analysis of the α, β and γ phases in poly(vinylidene fluoride) using FTIR. RSC Adv2017; 7: 15382–15389.
16.
NishiyamaTSumiharaTSatoE, et al.Effect of solvents on the crystal formation of poly(vinylidene fluoride) film prepared by a spin-coating process. Polym J2017; 49: 319–325.
17.
MartinsPSilvaMLanceros-MendezS. Determination of the magnetostrictive response of nanoparticles via magnetoelectric measurements. Nanoscale2015; 7: 9457–9461.
18.
AntipovaVOmelyanchikASobolevK, et al.Enhancing wettability and adhesive properties of PVDF-based substrates through non-thermal helium plasma surface modification. Polymer2024; 290: 126567.
19.
FanZSchwedesMSchwadererJ, et al.Molecular weight as a key for electroactive phase formation in poly(vinylidene fluoride). Materials Research Letters2022; 10: 271–277.
20.
MammeriF. Chapter 3 - nanostructured flexible PVDF and fluoropolymer-based hybrid films. Frontiers of Nanoscience2019; 14: 67–101.
21.
RamanaEVDurairajanAKavithaD, et al.Enhanced magnetoelectric and energy storage performance of strain-modified PVDF-Ba0.7Ca0.3TiO3-Co0.6Zn0.4Fe2O4 nanocomposites. J Energy Storage2024; 87: 111454.
22.
ChoiMHYangSC. CoFe2O4 nanofiller effect on β-phase formation of PVDF matrix for polymer-based magnetoelectric composites. Mater Lett2018; 223: 73–77.
23.
SupriyaSKumarLKarM. Optimization of dielectric properties of PVDF–CFO nanocomposites. Polym Compos2019; 40: 1239–1250.
24.
HayesPSchellVSalzerS, et al.Electrically modulated magnetoelectric AlN/FeCoSiB film composites for DC magnetic field sensing. J Phys D Appl Phys2018; 51: 354002.
25.
SreenivasuluGLaletinUPetrovVM, et al.A permendur-piezoelectric multiferroic composite for low-noise ultrasensitive magnetic field sensors. Appl Phys Lett2012; 100: 173506.
26.
ChuZDongCTuC, et al.A low-power and high-sensitivity magnetic field sensor based on converse magnetoelectric effect. Appl Phys Lett2019; 115: 162901.
27.
WangYLiJViehlandD. Magnetoelectrics for magnetic sensor applications: status, challenges and perspectives. Mater Today2014; 17: 269–275.
28.
NanTHuiYRinaldiM, et al.Self-biased 215MHz magnetoelectric NEMS resonator for ultra-sensitive DC magnetic field detection. Sci Rep2013; 3: 1985.
29.
MushtaqFTorlakcikHVallmajo-MartinQ, et al.Magnetoelectric 3D scaffolds for enhanced bone cell proliferation. Appl Mater Today2019; 16: 290–300.
30.
FersonNDUhlAMAndrewJS. Piezoelectric and magnetoelectric scaffolds for tissue regeneration and biomedicine: a review. IEEE Trans Ultrason Ferroelectrics Freq Control2021; 68(2): 229–241.
31.
DongSZhaiJLiJF, et al.Multimodal system for harvesting magnetic and mechanical energy. Appl Phys Lett2008; 93: 103511.
32.
OnutaT-DWangYLongCJ, et al.Energy harvesting properties of all-thin-film multiferroic cantilevers. Appl Phys Lett2011; 99: 203506.
33.
GüçlüHKasımHYaziciM. Investigation of the optimum vibration energy harvesting performance of electrospun PVDF/BaTiO3 nanogenerator. J Compos Mater2022; 57(3): 409–424.
34.
GrezesCEbrahimiFAlzateJG, et al.Ultra-low switching energy and scaling in electric-field-controlled nanoscale magnetic tunnel junctions with high resistance-area product. Appl Phys Lett2016; 108: 012403.
35.
BibesMBarthélémyA. Multiferroics: towards a magnetoelectric memory. Nat Mater2008; 7: 425–426.
36.
LiXLeeARazaviSA, et al.Voltage-controlled magnetoelectric memory and logic devices. MRS Bull2018; 43: 970–977.
37.
KumarRPandeyAKSinghR, et al.On nano polypyrrole and carbon nano tube reinforced PVDF for 3D printing applications: rheological, thermal, electrical, mechanical, morphological characterization. J Compos Mater2020; 54(29): 4677–4689.
38.
KosubTKopteMHühneR, et al.Purely antiferromagnetic magnetoelectric random access memory. Nat Commun2017; 8: 13985.
39.
SolomonIJSevvelPGunasekaranJ. A review on the various processing parameters in FDM. Mater Today Proc2021; 37: 509–514.
40.
MohammadpourfazeliSArashSAnsariA, et al.Future prospects and recent developments of polyvinylidene fluoride (PVDF) piezoelectric polymer; fabrication methods, structure, and electro-mechanical properties. RSC Adv2023; 13: 370–387.
41.
FerreiraACostaPCarvalhoH, et al.Extrusion of poly(vinylidene fluoride) filaments: effect of the processing conditions and conductive inner core on the electroactive phase content and mechanical properties. J Polym Res2011; 18: 1653–1658.
42.
NishiyamaTSumiharaTSasakiY, et al.Crystalline structure control of poly(vinylidene fluoride) films with the antisolvent addition method. Polym J2016; 48: 1035–1038.
43.
KimHtorresFVillagranD, et al.3D printing of BaTiO3/PVDF composites with electric in situ poling for pressure sensor applications. Macromol Mater Eng2017; 302: 1700229.
44.
PeiHXieYXiongY, et al.A novel polarization-free 3D printing strategy for fabrication of poly (Vinylidene fluoride) based nanocomposite piezoelectric energy harvester. Compos B Eng2021; 225: 109312.
45.
AmirovAOmelyanchikAMurzinD, et al.3D printing of PLA/Magnetic ferrite composites: effect of filler particles on magnetic properties of filament. Processes2022; 10: 2412.
46.
RibeiroCCostaCMCorreiaDM, et al.Electroactive poly(vinylidene fluoride)-based structures for advanced applications. Nat Protoc2018; 13: 681–704.
47.
OmelyanchikAMarquésJLRivasM, et al.A do-it-yourself approach for developing a magnetic field mapping setup using a 3D printer. Meas Sci Technol2023; 34(10): 107001.
48.
Hassanpour AmiriMSharifi DehsariHAsadiK. Magnetoelectric coupling coefficient in multiferroic capacitors: fact vs Artifacts. J Appl Phys2022; 132: 164102.
49.
DuongGVGroessingerRSchoenhartM, et al.The lock-in technique for studying magnetoelectric effect. J Magn Magn Mater2007; 316: 390–393.
50.
PurushothamanSMTroncoMFPoncotM, et al.Quantifying the crystalline polymorphism in PVDF: comparative criteria using DSC, WAXS, FT-IR, and Raman spectroscopy. ACS Appl Polym Mater2024; 14: 8291–8305.
51.
ShepelinNAGlushenkovAMLussiniVC, et al.New developments in composites, copolymer technologies and processing techniques for flexible fluoropolymer piezoelectric generators for efficient energy harvesting. Energy Environ Sci2019; 12: 1143–1176.
52.
LiJMengQLiW, et al.Influence of crystalline properties on the dielectric and energy storage properties of poly(vinylidene fluoride). J Appl Polym Sci2011; 122: 1659–1668.
53.
NakagawaKIshidaY. Annealing effects in poly(vinylidene fluoride) as revealed by specific volume measurements, differential scanning calorimetry, and electron microscopy. J Polym Sci Polym Phys Ed1973.
54.
MacconePBrinatiGArcellaV, et al.Environmental stress cracking of poly(vinylidene fluoride) in sodium hydroxide. Effect of chain regularity. Polym Eng Sci2000; 40: 761–767.
55.
Della GattaG. Standards, calibration, and guidelines in microcalorimetry. Part 2. Calibration standards for differential scanning calorimetry, 2006. (IUPAC Technical Report).
56.
MaríaNPatilYPolymeropoulosG, et al.(PVDF)2(PEO)2 miktoarm star copolymers: synthesis and isothermal crystallization leading to exclusive β-phase formation. Eur Polym J2022; 179(1): 111506.
57.
MartínJZhaoDLenzT, et al.Solid-state-processing of δ-PVDF. Mater Horiz2017; 4: 408–414.
58.
SatapathySPawarSGuptaPK, et al.Effect of annealing on phase transition in poly(vinylidene fluoride) films prepared using polar solvent. Bull Mater Sci2011; 34: 727–733.
59.
LiYLiaoCTjongSC. Electrospun polyvinylidene fluoride-based fibrous scaffolds with piezoelectric characteristics for bone and neural tissue engineering. Nanomaterials2019; 9.
60.
SureshGJatavSMallikarjunachariG, et al.Influence of microstructure on the nanomechanical properties of polymorphic phases of poly(vinylidene fluoride). J Phys Chem B2018; 122: 8591–8600.
61.
PalneediHAnnapureddyVPriyaS, et al.Status and perspectives of multiferroic magnetoelectric composite materials and applications. Actuators2016; 5: 9.
62.
GuptaRKotnalaRK. A review on current status and mechanisms of room-temperature magnetoelectric coupling in multiferroics for device applications. J Mater Sci2022; 57: 12710–12737.
63.
Alvarez-PerezMACirilloVPastore CarboneMG, et al.In vitro cell interactions on PVDF films: effects of surface morphology and polar phase transition. Materials2021; 14: 5232.
