Polymer-Nanoparticle Composites: From Synthesis to Modern Applications
Abstract
:1. Introduction
- optical and magnetic properties
- microelectronic devices
- piezoelectric actuators and sensors
- electrolytes, anodes in lithium-ion-batteries and supercapacitors
- organic solar cells and intrinsic conductive polymers
- photoresists used in microelectronics and microsystems technologies
- biomedical sciences.
- electrical and thermal conductivity
- polymer phase behavior and thermal stability
- mechanical properties like stiffness, Young’s modulus, wear, fatigue, and others
- flame retardancy [9]
- density
- physical properties such as magnetic, optic, or dielectric properties.
2. Special Features of Nanoparticles
2.1. Particle size dependent properties of inorganic nanoparticles
2.2. Polymer-nanoparticle interface
3. Composite Types
3.1. Polymer-matrix composites
3.2. Composite nanoparticles
Core | Shell | Synthesis Method | Ref. |
---|---|---|---|
Metal-oxides | Polymerizable | Microwave Plasma plus in situ coating | [39] |
HfO2, ZrO2, ZnO, Fe2O3, TiO2, Al2O3 | MMA; Fluoropolymers | Microwave Plasma plus in situ coating | [52] |
Fe2O3 | Modified PMMA | Microwave Plasma plus in situ coating | [40] |
Fe2O3 | Initiator plus styrene | Complex | [55] |
Al2O3 | Polyacrylic acid (PAA) | Commercial nanoparticles, layer by layer deposition with controlled polymer adsorption | [42] |
Al2O3 | Polyethylene (PE) | In situ Chemical Vapor Synthesis | [50] |
Al2O3 | Pyrrole | Ex situ deposition using plasma polymerization | [49] |
ZrO2 | PE | Ex situ by inductively coupled plasma polymerization | [51] |
TiO2 | PMMA | Ex situ deposition on commercial, nanoparticles by mixing with MMA solution and irradiation with electron beam | [47] |
TiO2 | PMMA | Ex situ by plasma polymerization | [46] |
TiO2 | Polystyrene (PS) | Ex situ by radical polymerization | [44] |
SiO2 | PS | SiO2 by Stöber synthesis; surface modification with coupling reagent; polymerization | [43] |
SiO2 | Acrylate based polymers | In situ Chemical Vapor Synthesis | [48] |
ZnO | Acrylic acid | Ex situ deposition using plasma polymerization | [45] |
Fe3O4 | ε-Caprolactone | Fe3O4 by alkaline hydrolysis, followed by surface functionalization with ultrasound; surface initiated ring opening polymerization | [53] |
Fe3O4 | ε-Caprolactone | Fe3O4 by alkaline hydrolysis, followed by surface functionalization; graft polymerization using microwaves | [54] |
Core | Shell | Synthesis Method | Ref. |
---|---|---|---|
TiO2 | C | Emulsion polymerization plus heat treatment | [56] |
C (micro-sized) | SnO2 | Sol-gel, using commercial graphite | [57] |
SnO2 | C | Thermal evaporation | [58] |
SnO2 | C | One-pot solvothermal synthesis and subsequent calcination | [59] |
3.3. Microsphere composite nanoparticles
4. Composite Formation Techniques
4.1. Ex situ processes
4.2. Chemical in situ methods
4.3. Physical in situ methods
4.4. Drawbacks in composite formation
- shear forces during compounding
- particle surface chemistry and polarity
- interaction between bulk polymer and interfacial-polymer layer as well as interaction between interfacial-polymer layer and ceramic nanoparticles.
5. Thermomechanical Composite Properties
- particle shape, agglomeration, and size distribution
- particle specific surface area and related surface chemistry
- particle-polymer matrix interface and interaction
- compounding method and related shear forces.
Item | Polymer-filler interaction | Impact |
---|---|---|
Elastic modulus | Attractive/repulsive | Increase with volume fraction |
Attractive/repulsive | Increase with size decrease | |
Density/volume | Attractive | Increased volume as size decreases |
Repulsive | n.a. | |
Glass transition temperature | Attractive | Increase with size decrease |
Repulsive | Level until 0.5%, drops off level from 1–10% |
Item | Polymer-filler interaction | Impact |
---|---|---|
Elastic modulus | Attractive/repulsive | Increase with volume fraction |
Attractive/repulsive | Increase with size decrease | |
Density/volume | Attractive | Increased volume as size decreases |
Repulsive | n.a. | |
Glass transition temperature | Attractive | Decrease with addition of particles |
Repulsive | n.a. | |
Crystallinity | Attractive/repulsive | No major effect |
5.1. Glass transition temperature and coefficient of thermal expansion
- the addition of ceramic fillers lowers the CTE
- an increase of TG can be observed if an attractive interaction of the nanofiller with the polymer matrix by physic- or chemisorption is given
- a decrease of TG occurs if the nanoparticle has a repulsive interaction with the matrix.
5.2. Elastic modulus, tensile strength, flexural strength and impact performance
5.3. Scratch resistance, wear and creep properties
6. Functional Properties and Applications of Nanocomposites
6.1. Optical properties
- especially in the case of TiO2 not all authors indicate the phase they use
- different units as wt % or vol % are used for the filler
- surface modified nanoparticles as well as pristine nanoparticles are used
- different particle sizes are used
- different processes for the synthesis of the composites are used
- the influence of remaining precursor residuals is unclear.
Nano-Filler | Diameter [nm] | Matrix | Δn, Refractive index increase | Reference |
---|---|---|---|---|
ZnS/PMAA + acetic acid; 50 vol % | ZnS: 3 nm | DMAA/St/DVB | 0.023 | [78] |
ZrO2 50 wt % TiO2 42 wt % | 5 nm 7 nm | PC PC | 0.067 (at 589 nm) 0.135 (at 589 nm) | [142] |
TiO2, 60 wt % | Amorphous | Epoxy | 0.221 | [143] |
ME-capped ZnS 30 wt % | ZnS: 3 nm | DMAA/St/DVB | 0.048 | [87] |
TiO2 27.3 vol % TiO2 90 vol % | <10 nm | PS | 0.22 0.41 | [144] |
TiO2 acetic acid mod. 10 wt % 30 wt % | ~ 15 +/- 10 nm | Epoxy | 0.71 (at 633 nm) 0.9 (at 633 nm) | [145] |
TiO2, 50 wt % | Anatase: 4 nm | Organic silica sol | 0.163 (at 633 nm) | [146] |
ZrO2, 5 wt % | 5 – 25 nm | TMP-TGE | 0.1 (at 631 nm) | [147] |
TiO2 surface modified 80 wt % 80 wt % | TiO2: 3 – 6 nm | PHE PSTMA | 0.23 (at 589 nm) 0.19 (at 633 nm) | [148] |
TiO2, 65 wt % | amorphous | Epoxy | 0.187 (at 633 nm) | [149] |
PbS, 41.8 wt % | <10 nm | Polythiourethane | 0.481 (at 633 nm) | [150] |
Al2O3-C®, 1 wt % ZrO2 VP®, 0.2 wt % | 13 nm 30 nm | PMMA | 0.0016 (at 633 nm) 0.0014 (at 633 nm) | [95] |
TiO2, 35 wt % (=10.5 vol %) | Rutile: 2.5 nm | PVAL | 0.088 (at 589 nm) | [151] |
Al2O3-C®, 1 wt % | 13 nm | High temperature stable PC | 0.0043 (at 633 nm) 0.0031 (at 1550 nm | [152] |
SiO2, 10 wt % Al2O3-C®, 1 wt % Al2O3, 0.5 wt % | 12 nm 13 nm 38 nm | PMMA PMMA PMMA | -0.007 (at 633 nm) 0.007 (at 633 nm) 0.004 (at 633 nm) | [94,96] |
ZnO, 7.76 vol % | 22 nm | PMMA | 0.02 (at 633 nm) | [153] |
6.2. Magnetic properties
6.3. Microelectronic devices
- huge functionality like large capacitance values in case of integrated capacitors
- process compatibility to industrial PCB-fabrication
- abandonment of lead-containing materials
- low overall costs
- high reliability and extended life cycle.
6.4. Piezoelectric actuators and sensors
6.5. Lithium-ion batteries
- mechanical and chemical stability of the used electrode and electrolyte materials
- huge energy storage capability
- wide temperature range of operation (-40–85 °C)
- negligible self-discharge
- flat shape of the discharge curve
- short charge time
- long cycle life time with almost unchanged capacity
- low costs
- enhanced safety especially inflammability.
- anode: pure lithium metal or more common graphite
- cathode: spinel-type lithium-metal oxides like LiCoO2 or LiMn2O4
- electrolyte: highly polar, aprotic low-viscous organic solvents mixtures containing a conducting salt like LiClO4, LiPF6 or LiBF4
- separator: physical barrier between the electrodes avoiding short-circuit and supporting a mechanical stability, consisting of a porous inert material filled with e.g., a polymer-gel.
6.5.1. Polymer-nanocomposite electrolytes applying passive ceramic nanofillers
6.5.2. Polymer-nanocomposite electrolytes applying active ceramic nanofillers
6.5.3. Nanocomposites as electrodes and supercapacitors
- a barrier to suppress the aggregation of active particles
- a buffering matrix to relax the volume expansion during the lithiation/delithiation process
- an improvement of the conductance of the electronic material.
6.6. Organic solar cells and intrinsic conductive polymer nanocomposites
6.7. Polymer-nanocomposite-photoresists
- improved sensitivity to electromagnetic radiation of a certain wavelength region
- improved resolution
- improved chemical resist stability
- improved mechanical stability during processing
- tailoring of the coefficient of thermal expansion
- introduction of new functionalities like electrical conductivity or magnetic properties
- direct fabrication of microstructured ceramic or metal components via microstereo-lithography (rapid prototyping).
Material | Initial specific capacity [mAh/g] | # cycles/capacity retention | # cycles/capacity retention | # cycles/capacity retention | Ref. |
---|---|---|---|---|---|
Pure graphite (C) | 300 | 10/100 % | 30/99.1 % | 50/97.8 % | [228] |
Bulk SnO2 | 652 | 10/63 % | 30/49.8 % | 50/31.7 % | [228] |
4 wt % SnO2 in C | 342 | 10/99.6 % | 30/96.6 % | 50/88 % | [228] |
9.8 wt % SnO2 in C | 384 | 10/99.4 % | 30/96.3 % | 50/88.3 % | [228] |
16.5 wt % SnO2 in C | 428 | 10/99.2 % | 30/90.1 % | 50/72.4 % | [228] |
14.2 wt % SnO2 in C | 465 | 40/90 % | 60/80 % | [229] | |
14.9 wt % SnO2 in C | 472 | 40/89 % | 60/75 % | [229] | |
14.4 wt % SnO2 in C | 460 | 40/74 % | 60/56 % | [229] | |
TiO2 | n.a. | 10/67.5 % | [56] | ||
TiO2/C (87/13) | 122 | 10/96.7 % | [56] | ||
SnO2/PPy (81.75/18.25) | 562 | 20/70 % | [230] | ||
SnO2 | 570 | 20/40 % | [230] | ||
SnO2/graphite | 633 | 30/57 % | [57] | ||
SnO2 at C | 667 | 18/55 % | 30/55 % | 40/55 % | [59] |
TNHCs | 831 | 10/>96 % | >100/66.2 % | [65] | |
SnO2/C (75/25) | 993 | 50/62 % | 200/62 % | [231] | |
SnO2/graphene (40/60) | 765 | 100/66.9 % | [232] |
6.8. Biomedical sciences
- bone fracture repair: Epoxide-carbon fibers-composite for external fixators
- bone plates and screws: Epoxide, PMMA, polypropylene, polyethylene, PS, Nylon, polybutylterephthalate, PEEK, reinforced with carbon fibers
- joints replacement: Ultrahigh molecular weight polyethylene or PEEK-carbon fibers composites for total hip replacement
- bone cement: PMMA-glass powder
- dental applications: Acrylates, filled with surface modified nanosized SiO2 or ZrO2
- catheters: Urethanes or silicone rubber, reinforced with nanosized SiO2
- prosthetic limbs: Thermosets, reinforced with glass, carbon, or Kevlar fibers.
7. Summary
- Size dependent physical properties of the nanoparticles used
- Particle agglomeration
- Maximum accessible shear forces during compounding affects composite properties
- Reproducibility and comparability of composite formation techniques
- Influence of additives like surfactants, plasticizers, and others, on the composite properties
- Beyond target property: side effects on the flow behavior, thermal stability, and others
- Low cost device fabrication by e.g., suitable shaping methods possible?
Acknowledgements
References and Notes
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Hanemann, T.; Szabó, D.V. Polymer-Nanoparticle Composites: From Synthesis to Modern Applications. Materials 2010, 3, 3468-3517. https://doi.org/10.3390/ma3063468
Hanemann T, Szabó DV. Polymer-Nanoparticle Composites: From Synthesis to Modern Applications. Materials. 2010; 3(6):3468-3517. https://doi.org/10.3390/ma3063468
Chicago/Turabian StyleHanemann, Thomas, and Dorothée Vinga Szabó. 2010. "Polymer-Nanoparticle Composites: From Synthesis to Modern Applications" Materials 3, no. 6: 3468-3517. https://doi.org/10.3390/ma3063468