Photocurable Carbon Nanotube/Polymer Nanocomposite for the 3D Printing of Flexible Capacitive Pressure Sensors.

A photocurable resin/carbon nanotube (CNT) nanocomposite was fabricated from aligned CNTs in an acrylic matrix. The conductivity of the nanocomposite increased rapidly and then stabilized when the CNT content was increased up to and beyond the percolation threshold. Various structures were created using a digital light processing (DLP) 3D printer. Various polymeric dispersants (SMA-amide) were designed and synthesized to improve the CNT dispersion and prevent aggregation. The benzene rings and lone electron pairs on the dispersant interacted with aromatic groups on the CNTs, causing the former to wrap around the latter. This created steric hindrance, thereby stabilizing and dispersing the CNTs in the solvent. CNT/polymer nanocomposites were created by combining the dispersant, CNTs, and a photocurable resin. The CNT content of the nanocomposite and the 3D printing parameters were tuned to optimize the conductivity and printing quality. A touch-based human interface device (HID) that utilizes the intrinsic conductivity of the nanocomposite and reliably detects touch signals was fabricated, enabling the free design of sensors of various styles and shapes using a low-cost 3D printer. The production of sensors without complex circuitry was achieved, enabling novel innovations.

Graphene Nanoplatelet/Multiwalled Carbon Nanotube/Polypyrrole Hybrid Fillers in Polyurethane Nanohybrids with 3D Conductive Networks for EMI Shielding.

This work reports the preparation of graphene nanoplatelet (GNP)/multiwalled carbon nanotube (MWCNT)/polypyrrole (PPy) hybrid fillers via in situ chemical oxidative polymerization with the addition of a cationic surfactant, hexadecyltrimethylammonium bromide. These hybrid fillers were incorporated into polyurethane (PU) to prepare GNP/MWCNT/PPy/PU nanohybrids. The electrical conductivity of the nanohybrids was synergistically enhanced by the high conductivity of the hybrid fillers. Furthermore, the electromagnetic interference (EMI) shielding effectiveness (SE) was greatly increased by interfacial polarization between the GNPs, MWCNTs, PPy, and PU. The optimal formulation for the preparation of GNP/MWCNT/PPy three-dimensional (3D) nanostructures was determined by optimization experiments. Using this formulation, we successfully prepared GNP/PPy nanolayers (two-dimensional) that are extensively covered by MWCNT/PPy nanowires (one-dimensional), which interconnect to form GNP/MWCNT/PPy 3D nanostructures. When incorporated into a PU matrix to form a nanohybrid, these 3D nanostructures form a continuous network of conductive GNP-PPy-CNT-PPy-GNP paths. The EMI SE of the nanohybrid is 35-40 dB at 30-1800 MHz, which is sufficient to shield over 99.9% of electromagnetic waves. Therefore, this EMI shielding material has excellent prospects for commercial use. In summary, a nanohybrid with excellent EMI SE performance was prepared using a facile and scalable method and was shown to have great commercial potential.

Flexible Hybrid Electronics Nanofiber Electrodes with Excellent Stretchability and Highly Stable Electrical Conductivity for Smart Clothing.

In this paper, a side-by-side, dual-nozzle electrospinning process was used to prepare a flexible hybrid electronics (FHE) material with excellent stretchable properties. A highly stable electrical conductivity was also imparted to the resulting membrane electrodes using silver nanoparticles (AgNPs) and carbon-based nanomaterials of different structures. The AgNP/carbon-based nanomaterials were coated onto bicomponent polymer nanofibers (composed of polyurethane (PU) and polyvinylidene difluoride (PVDF)) on the nanofiber membrane. The FHE nanofiber electrodes were finally integrated into clothing designed to accurately measure human body sensing signals (e.g., electrocardiography (ECG) and electromyography (EMG) signals). To effectively increase the high electrical conductivity, a polymer-type dispersant (polyisobutylene-b-poly(oxyethylene)-b-polyisobutylene, a triblock copolymer) was used to effectively and stably disperse AgNPs with different particle sizes and carbon-based nanomaterials with different geometric dimensions (e.g., zero-dimensional carbon black, one-dimensional carbon nanotubes, and two-dimensional graphene) through non-covalent adsorption. Moreover, the bicomponent PVDF-PU nanofibers were immersed in a mixed dispersant of AgNPs and carbon-based nanomaterials at low concentrations, and thermal post-treatment was conducted to improve the electrical conductivity. The AgNP/graphene oxide (GO) nanofiber electrode exhibited a continuous phase with a stable material microstructure after 5000 repetitions of 50% tension-tension fatigue testing. The waveform pattern obtained from the proposed AgNP/GO nanofiber electrode was compared with those of traditional ECG and EMG electrodes. The nanofiber web electrode treated with organic/inorganic mixed dispersants and verified via tests of its electrical and fatigue properties was found to be suitable for long-term ECG and EMG monitoring, and it has excellent potential in wearable smart sensors.

Highly Thermally Conductive Epoxy Composites with AlN/BN Hybrid Filler as Underfill Encapsulation Material for Electronic Packaging.

In this study, the effects of a hybrid filler composed of zero-dimensional spherical AlN particles and two-dimensional BN flakes on the thermal conductivity of epoxy resin were studied. The thermal conductivity (TC) of the pristine epoxy matrix (EP) was 0.22 W/(m K), while the composite showed the TC of 10.18 W/(m K) at the 75 wt% AlN-BN hybrid filler loading, which is approximately a 46-fold increase. Moreover, various essential application properties were examined, such as the viscosity, cooling rate, coefficient of thermal expansion (CTE), morphology, and electrical properties. In particular, the AlN-BN/EP composite showed higher thermal stability and lower CTE (22.56 ppm/°C) than pure epoxy. Overall, the demonstrated outstanding thermal performance is appropriate for the production of electronic packaging materials, including next-generation flip-chip underfills.

Hydrophilic-Hydrophobic Nanohybrids of AuNP-Immobilized Two-Dimensional Nanomica Platelets as Flexible Substrates for High-Efficiency and High-Selectivity Surface-Enhanced Raman Scattering Microbe Detection.

A flexible hybrid substrate was developed by affixing gold nanoparticles (AuNPs) onto the surface of two-dimensional nanomica platelets (NMPs). The substrate was successfully used in biosensors with high efficiency and high selectivity through surface-enhanced Raman scattering (SERS). By controlling the amphiphilicity of the hybrid substrate, the flexible substrate was made highly selective toward biomolecules. Four different SERS substrate systems were constructed, including intercalated mica, exfoliated NMPs, hydrophilic exfoliated NMPs, and hydrophobic exfoliated NMPs. NMPs were only 1 nm thick. AuNPs adsorbed on both sides of NMPs and thus created excellent three-dimensional hot junction effects in the z-axis direction. For the detection of adenine in DNA, a satisfactory Raman enhancement factor (EF) of up to 8.9 × 106 was achieved with the detection limit as low as 10-8 M. Subsequently, the AuNP/NMP hybrids were adopted to rapidly detect hydrophilic Staphylococcus hominis and hydrophobic Escherichia coli. The AuNP/PIB-POE-PIB/NMP nanohybrid was concurrently hydrophilic and hydrophobic. This amphiphilic property greatly enhanced the detection selectivity and signal intensity for hydrophilic or hydrophobic bacteria. Overall, AuNPs/PIB-POE-PIB/NMPs developed as SERS substrates enable rapid, sensitive biodetection.

Immobilization of Air-Stable Copper Nanoparticles on Graphene Oxide Flexible Hybrid Films for Smart Clothes.

Through the use of organic/inorganic hybrid dispersants-which are composed of polymeric dispersant and two-dimension nanomaterial graphene oxide (GO)-copper nanoparticles (CuNPs) were found to exhibit nano stability, air-stable characteristics, as well as long-term conductive stability. The polymeric dispersant consists of branched poly(oxyethylene)-segmented esters of trimellitic anhydride adduct (polyethylene glycol-trimethylolpropane-trimellitic anhydride, designated as PTT). PTT acts as a stabilizer for CuNPs, which are synthesized via in situ polymerization and redox reaction of the precursor Cu(CH3COO)2 within an aqueous system, and use graphene oxide to avoid the reduction reaction of CuNPs. The results show that after 30 days of storage the CuNPs/PTT/GO composite film maintains a highly conductive network (9.06 × 10-1 Ω/sq). These results indicate that organic/inorganic PTT/GO hybrid dispersants can effectively maintain the conductivity stability of CuNPs and address the problem of CuNP oxidation. Finally, the new CuNPs/PTT/GO composite film was applied to the electrocardiogram (ECG) smart clothes. This way, a stable and antioxidant-sensing electrode can be produced, which is expected to serve as a long-term ECG monitoring device.

Piezoelectric Property Enhancement of PZT/Poly(vinylidenefluoride-co-trifluoroethylene) Hybrid Films for Flexible Piezoelectric Energy Harvesters.

In this study, lead zirconate titanate (PZT) ceramic particles were added for further improvement. PZT belongs to the perovskite family and exhibits good piezoelectricity. Thus, it was added in this experiment to enhance the piezoelectric response of the poly(vinylidenefluoride-co-trifluoroethylene) (PVDF-TrFE) copolymer, which produced a voltage output of 1.958 V under a cyclic pressure of 290 N. In addition, to further disperse the PZT particles in the PVDF-TrFE matrix, tetradecylphosphonic acid (TDPA) was synthesized and employed to modify the PZT surface, after which the surface-modified PZT (m-PZT) particles were added to the PVDF-TrFE matrix. The TDPA on the PZT surface made it difficult for the particles to aggregate, allowing them to disperse in the polymer solution more stably. In this way, the PZT particles with piezoelectric responses could be uniformly dispersed in the PVDF-TrFE film, thereby further enhancing its overall piezoelectric response. The test results showed that upon the addition of 10 wt % m-PZT, the piezoelectric coefficient of m-PZT/PVDF-TrFE 10 wt % was 27 pC/N; and under a cyclic pressure of 290 N, the output voltage reached 3.426 V, which demonstrated a better piezoelectric response than the polymer film with the original PZT particles. Furthermore, the piezoelectric coefficient of m-PZT/PVDF-TrFE 10 wt % was 27.1 pC/N. This was exhibited by maintaining a piezoelectric coefficient of 26.8 pC/N after 2000 cycles. Overall, a flexible piezoelectric film with a high piezoelectric coefficient was prepared by following a simple fabrication process, which showed that this film possesses great commercial potential.

Polymer-Assisted Dispersion of Boron Nitride/Graphene in a Thermoplastic Polyurethane Hybrid for Cooled Smart Clothes.

The avoidance and mitigation of energy wastage have attracted increasing attention in the context of global warming and climate change. With advances in materials science, diverse multifunctional materials with high thermal conductivity have shown excellent energy-saving potential. In this study, a hybrid film exhibiting high thermal conductivity with excellent stretchability and washability was prepared. First, a simple surface modification of boron nitride (BN) was performed to realize a modified boron nitride (BNOH) filler. Next, an organic dispersant was synthesized to enhance the dispersion of BNOH and graphene nanoplatelets (GNPs) in the proposed composite. Subsequently, a simple procedure was used to combine the dispersed GNPs and BNOH fillers with thermoplastic polyurethane (TPU) to fabricate a hybrid structure. The hybrid films composed of BNOH-GNP/TPU with a dispersant exhibited a high thermal conductivity of 12.62 W m-1 K-1 at a low filler loading of 20 wt.%. This hybrid film afforded excellent stretchability and washability, as indicated by the very small thermal-conductivity reduction to only 12.23 W m-1 K-1 after 100 cycles of fatigue testing and to 12.01 W m-1 K-1 after 10 washing cycles. Furthermore, the cooling and hydrophobicity properties of the hybrid film were enhanced when compared with neat TPU. Overall, our approach demonstrates a simple and novel strategy to break the passive effect of traditional commercial cooling clothing by combining a high-thermal-conductivity film with an active cooling source to amplify the cooling effect and develop wearable cooled smart clothes with great commercial potential.

Enhanced Efficiency of Dye-Sensitized Solar Cells Based on Polymer-Assisted Dispersion of Platinum Nanoparticles/Carbon Nanotubes Nanohybrid Films as FTO-Free Counter Electrodes.

In this study, polymer-assisted dispersants are used to stabilize the nanohybrids of platinum nanoparticles (PtNPs)/carbon nanotubes (CNTs) through non-covalent bond forces. These dispersants aim to replace the florine-doped tin oxide (FTO) glass in traditional dye-sensitized solar cells (DSSCs) as counter electrodes. The large specific surface area, high conductivity, and redox potential of PtNPs/CNT nanohybrids are used as the basis to utilize them as the counter electrode material to fabricate a dye-sensitized solar cell. The conductivity results indicate that the resistance of the PtNP/CNT nanohybrid film can be reduced to 7.25 Ω/sq. When carbon nanotubes are mixed with platinum nanoparticles at a weight ratio of 5/1, the photoelectric conversion efficiency of DSSCs can reach 6.28%. When using the FTO-containing substrate as the counter electrode, its conversion efficiency indicates that the micro-/nano-hybrid material formed by PtNPs/CNTs also exhibits an excellent photoelectric conversion efficiency (8.45%) on the traditional FTO substrate. Further, a large-area dye-sensitive cell is fabricated, showing that an 8 cm × 8 cm cell has a conversion efficiency of 7.95%. Therefore, the traditional Pt counter electrode can be replaced with a PtNP/CNT nanohybrid film, which both provides dye-sensitive cells with a high photoelectric conversion efficiency and reduces costs.

Enhanced Piezoelectric Properties of Poly(Vinylidenefluoride-Co-Trifluoroethylene)/Carbon-Based Nanomaterial Composite Films for Pressure Sensing Applications.

In this study, heat and polarization treatments were applied to poly(vinylidenefluoride-co-trifluoroethylene (PVDF-TrFE) films to improve their crystallinity and piezoelectric effect. Carbon-based nanomaterials (CBNs) of multiple dimensions (i.e., modified zero-dimensional (0D) carbon black (OCB), one-dimensional (1D) modified carbon nanotubes (CNT-COOH) and two-dimensional (2D) graphene oxide (GO)) were added to the copolymer to study the effects of different CBN dimensions on the crystallinity and piezoelectric effect of PVDF-TrFE films. Additionally, amphiphilic polymeric dispersants were added to improve the dispersibility of CBNs; the dispersant was synthesized by the amidation, and imidization reactions of styrene-maleic anhydride copolymer (SMAz) and polyoxyalkylene amine (M1000). Polymer solutions with different ratios of CBN to dispersant (z = 10:1, 5:1, 1:1, 1:5, 1:10) were prepared. The enhanced dispersibility enabled the fluorine atoms in the PVDF-TrFE molecular chain to more efficiently form hydrogen bonds with the -COOH group in the CBN, thereby increasing the content of the ß crystal phase (the origin of the piezoelectric effect) of the film. Therefore, the resulting film exhibited a higher output voltage on the application side and better sensitivity on the sensing element. The addition of CNT-COOH and polymeric dispersants increased the ß-phase content in PVDF-TrFE from 73.6% to 86.4%, which in turn raised the piezoelectric coefficient from 19.8 ± 1.0 to 26.4 ± 1.3 pC/N. The composite film-based pressure sensor also exhibited a high degree of sensitivity, which is expected to have commercial potential in the future.

Polyurethane/Nanosilver-Doped Halloysite Nanocomposites: Thermal, Mechanical Properties, and Antibacterial Properties.

In this study, the researchers successfully embellished the surface of halloysite (Ag/HNTs) with silver using halloysite, silver nitrate (AgNO3), and polyvinylpyrrolidone (PVP). The researchers then prepared polyurethane that contained pyridine ring by using 4,4'-diphenylmethane diisocyanate (MDI) and polytetramethylene glycol (PTMG) as the hard chain segment and the soft chain segment of polyurethane (PU), as well as 2,6-pyridinedimethanol (2,6-PDM) as the chain extension agent. This was followed by the preparation of Ag/HNTs/PUs nanocomposite thin films, achieved by mixing Ag/HNTs with different ratios into polyurethane that contains pyridine ring. First, the Ag/HNTs powders were analyzed using energy-dispersive X-ray spectroscopy, X-ray diffraction, and transmission electron microscopy. Subsequently, Fourier-transform infrared spectroscopy was used to examine the dispersibility of Ag/HNTs in PU, whereas the thermal stability and the viscoelasticity of Ag/HNTs/PU were examined using thermal gravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. When the mechanical properties of Ag/HNTs/PU were tested using a universal strength tester, the results indicated a maximum increase of 109.5% in tensile strength. The researchers then examined the surface roughness and the hydrophobic ability of the Ag/HNTs/PU thin films by using atomic force microscopy and water contact angle. Lastly, antibacterial testing on Escherichia coli revealed that when the additive of Ag/HNTs reached 2.0 wt%, 99.3% of the E. coli were eliminated. These results indicated that the addition of Ag/HNTs into PU could enhance the thermal stability, mechanical properties, and antibacterial properties of PU, implying the potential of Ag/HNTs-02 as biomedicine material.

Controlling the Structures, Flexibility, Conductivity Stability of Three-Dimensional Conductive Networks of Silver Nanoparticles/Carbon-Based Nanomaterials with Nanodispersion and their Application in Wearable Electronic Sensors.

This research has successfully synthesized highly flexible and conductive nanohybrid electrode films. Nanodispersion and stabilization of silver nanoparticles (AgNPs) were achieved via non-covalent adsorption and with an organic polymeric dispersant and inorganic carbon-based nanomaterials-nano-carbon black (CB), carbon nanotubes (CNT), and graphene oxide (GO). The new polymeric dispersant-polyisobutylene-b-poly(oxyethylene)-b-polyisobutylene (PIB-POE-PIB) triblock copolymer-could stabilize AgNPs. Simultaneously, this stabilization was conducted through the addition of mixed organic/inorganic dispersants based on zero- (0D), one- (1D), and two-dimensional (2D) nanomaterials, namely CB, CNT, and GO. Furthermore, the dispersion solution was evenly coated/mixed onto polymeric substrates, and the products were heated. As a result, highly conductive thin-film materials (with a surface electrical resistance of approximately 10-2 Ω/sq) were eventually acquired. The results indicated that 2D carbon-based nanomaterials (GO) could stabilize AgNPs more effectively during their reductNion and, hence, generate particles with the smallest sizes, as the COO- functional groups of GO are evenly distributed. The optimal AgNPs/PIB-POE-PIB/GO ratio was 20:20:1. Furthermore, the flexible electrode layers were successfully manufactured and applied in wearable electronic sensors to generate electrocardiograms (ECGs). ECGs were, thereafter, successfully obtained.

Adsorption Performance for Reactive Blue 221 Dye of ß-Chitosan/Polyamine Functionalized Graphene Oxide Hybrid Adsorbent with High Acid-Alkali Resistance Stability in Different Acid-Alkaline Environments.

A hybrid material obtained by blending ß-chitosan (CS) with triethylenetetramine-functionalized graphene oxide (TFGO) (CSGO), was used as an adsorbent for a reactive dye (C.I. Reactive Blue 221 Dye, RB221), and the adsorption and removal performances of unmodified CS and mix-modified CSGO were investigated and compared systematically at different pH values (2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12). The adsorption capacities of CS and CSGO were 45.5 and 56.1 mg/g, respectively, at a pH of 2 and 5.4 and 37.2 mg/g, respectively, at a pH of 12. This indicates that TFGO was successfully introduced into CSGO, enabling π-π interactions and electrostatic attraction with the dye molecules. Additionally, benzene ring-shaped GO exhibited a high surface chemical stability, which was conducive to maintaining the stability of the acid and alkali resistance of the CSGO adsorbent. The RB221 adsorption performance of CS and CSGO at acidic condition (pH 3) and alkaline condition (pH 12) and different temperatures was investigated by calculating the adsorption kinetics and isotherms of adsorbents. Overall, the adsorption efficiency of CSGO was superior to that of CS; thus, CSGO is promising for the treatment of dye effluents in a wide pH range.

Synthetic Environmentally Friendly Castor Oil Based-Polyurethane with Carbon Black as a Microphase Separation Promoter.

This study created water polyurethane (WPU) prepolymer by using isophorone diisocyanate, castor oil, dimethylolpropionic acid, and triethanolamine (TEA) as the hard segment, soft segment, hydrophilic group, and neutralizer, respectively. TEA, deionized water, and carbon black (CB) were added to the prepolymer under high-speed rotation to create an environmentally friendly vegetable-oil-based polyurethane. CB served as the fortifier and promoter of microphase separation. Fourier transform infrared spectroscopy was performed to elucidate the role of H-bond interactions within the CB/WPUs. Additionally, atomic force microscopy was conducted to determine the influence of H-bond interactions on the degree of microphase separation in the WPU. Furthermore, this study used four-point probe observation to discover the materials' conductivity of CB in the WPU. Thermogravimetric analysis and dynamic mechanical analysis were performed to measure the thermal properties of the CB/WPUs. The mechanical properties of CB/WPUs were measured using a tensile testing machine. The CB/WPUs were also soaked in 1 wt.% NaOH solution for different amounts of time to determine the degradation properties of the CB/WPUs. Finally, scanning electron microscopy was performed to observe the topography of the CB/WPUs after degradation.

Properties and degradation of castor oil-based fluoridated biopolyurethanes with different lengths of fluorinated segments.

To develop a durable, biodegradable polymer, this study successfully synthesized a castor-oil-based prepolymer by using methylene diphenyl diisocyanate as a hard segment, polycaprolactone as a soft segment, and castor oil as a functional monomer. We added perfluorinated alkyl segments with varying chain lengths into the castor-oil-based polymer to synthesize castor-oil-based fluoridated biopolyurethanes (FCOPUs) with different fluorinated segment lengths. The castor-oil-based polyurethanes with different fluorinated segment lengths had similar molecular weights, which enabled accurate analysis of the effect of the lengths of fluorinated segments on FCOPUs. Nuclear magnetic resonance (NMR) was used to perform 1H NMR, 19F NMR, 19F-19F COSY, 1H-19F COSY, and HMBC analyses on the FCOPU structures. The results of Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy curve fitting verified the interaction between C-F⋯H-N and C-F⋯C[double bond, length as m-dash]O. This interaction increased as the fluorinated segments became longer. Regarding the thermal properties of the FCOPUs, the thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis results revealed that long fluorinated segments were associated with increased thermal stability in the FCOPUs. The atomic force microscopy and tensile strength test suggested that long fluorinated segments contained in the FCOPUs increased the degree of phase separation and tensile strength in FCOPUs. Finally, we dipped the FCOPUs in a 3 wt% NaOH solution, calculated the weight loss of the FCOPUs, and observed their surface structure by using scanning electron microscopy.

Synthesis and Properties of Novel Polyurethanes Containing Long-Segment Fluorinated Chain Extenders.

In this study, novel biodegradable long-segment fluorine-containing polyurethane (PU) was synthesized using 4,4'-diphenylmethane diisocyanate (MDI) and 1H,1H,10H,10H-perfluor-1,10-decanediol (PFD) as hard segment, and polycaprolactone diol (PCL) as a biodegradable soft segment. Nuclear magnetic resonance (NMR) was used to perform ¹H NMR, 19F NMR, 19F⁻19F COSY, ¹H⁻19F COSY, and HMBC analyses on the PFD/PU structures. The results, together with those from Fourier transform infrared spectroscopy (FTIR), verified that the PFD/PUs had been successfully synthesized. Additionally, the soft segment and PFD were changed, after which FTIR and XPS peak-differentiation-imitating analyses were employed to examine the relationship of the hydrogen bonding reaction between the PFD chain extender and PU. Subsequently, atomic force microscopy was used to investigate the changes in the microphase structure between the PFD chain extender and PU, after which the effects of the thermal properties between them were investigated through thermogravimetric analysis, differential scanning calorimetry, and dynamic mechanical analysis. Finally, the effects of the PFD chain extender on the mechanical properties of the PU were investigated through a tensile strength test.