Technologies and Processes at the Nanoscale (TPNE)

TITLE: Nano-Reinforced Composites / HDPE-CNTs Composites / Shape Memory Materials reinforced with CNTs /
Nanocomposites manufactured by 3D Printing

DATE: 17.05.2022
NAME: Guilherme José de Antunes e Sousa
 Technologies and Processes at the Nanoscale (TPNE)

RESUME
• Nano-Reinforced Composites

A reinforcement and a matrix make up a composite material. Composites can be classed

according on their matrix or reinforcement. Polymer nanocomposites have applications in sensitive
equipment, information technology, transportation systems, and energy. Scientists are interested in using
nano-scaled fillers in polymer matrices because they can achieve possibly unique features due to
nanometric dimensions. Carbon nanotubes (CNTs) offer a lot of promise for improving polymer
mechanical, physical, and electrical properties. They have a very high aspect ratio combined with a low
density, as well as great strength and stiffness. The most important thing is to transfer the CNTs' potential
mechanical, thermal, and electrical capabilities to the polymer composite.
To effectively improve the material properties of polymers by adding CNTs as filler, two major
difficulties must be addressed: interfacial bonding and appropriate dispersion of individual CNTs in the
polymeric matrix. Chemical functionalization of the nanotube surface can improve interfacial adhesion to
the polymer. Nano-scaled particles have a massive surface area that is several orders of magnitude bigger
than ordinary fillers. This surface area serves as a stress transmission interface, but it is also responsible
for the CNTs' strong desire to aggregate. Their uniform dispersion in the matrix, agglomeration break-up,
and excellent wetting with the polymer are all required for successful utilization of their characteristics in
polymers.
A resin's low viscosity allows particles to be ordered by the resin. In this situation, due to
intermolecular interactions such as van der Waals forces, a large specific surface area already favors the
formation of agglomerates. Controlling surface polarity and the resulting interaction forces between
particles and matrix is required to prevent agglomeration. This can be accomplished by manipulating the
surface polarity, chemically functionalizing the particle surface, and forming covalent bonds or polar
contacts between the resin and the CNT. Functional compounds like carboxyl, carbonyl, and hydroxyl
introduce flaws in the graphite walls of CNTs, lowering their strength and stiffness.
CNTs are frequently entangled throughout the manufacturing process, but they must be evenly
distributed in the composite matrix. The degree of entanglement is determined by the CNT type and
manufacturing method. Only by improving the CNT/matrix interfacial interaction can a visible
reinforcement of the matrix with nanotubes and, more importantly, an improvement in fracture strength
be accomplished. Surfactants are another frequent way for assimilation of the polarity of CNT and matrix,
in addition to direct chemical functionalization. The physical attachment of this technique has the
advantage of not reducing the structural quality of CNTs. If CNTs are to be distributed equally in the
matrix polymer, five problems must be overcome: tube length, entanglement, volume percentage, high
matrix viscosity, and tube/tube attraction.
• HDPE-CNTs Composites

Constant stirring, surfactant-assisted processing, solution-evaporation methods with high-energy

sonication, and covalent functionalization of nanotubes with a polymer matrix are among the strategies
reported in the literature to produce homogeneous distribution of CNTs in the polymer matrix.
Mechanical qualities improve when CNT concentration rises, which is thought to be owing to a favorable
interface between polymer and CNT, which transfers load from polymer to CNT.
The total enthalpy of crystallization is increased when CNT is added to HDPE. The melting
point of composites is unaffected by CNT reinforcement in HDPE.
With the inclusion of CNTs, the crystallinity of the composite increases significantly. It demonstrates that
CNT serve as nucleation sites for polymer crystallization.
An increase in polymer crystallinity indicates that the CNT surface has a crystalline polymer
covering with a constant average thickness for each nanotube, indicating that the polymer–nanotube
interface is identical in all samples utilized in this investigation.
• Shape Memory Materials reinforced with CNTs

SMM (Shape-Memory Materials) are currently used solutions for active control, shape control,
and morphing. They can be metallic alloys (SMAs), piezoelectric, and polymers such as polyurethanes
 Technologies and Processes at the Nanoscale (TPNE)

(SMPUs). Carbon nanotubes (CNTs) added to SMPU appear to improve its overall properties, with a lot
of promise in terms of improved shape memory.
In situ polymerization and mechanical melt mixing are the two basic methods for creating
SMPU/CNT nanocomposites. Shape memory polymers (SMPs), a new family of shape memory materials
that can be deformed and kept in a transitory shape until receiving a unique stimulus or trigger, have
gotten a lot of attention in this field. Polyurethanes are one of the most important types of SMPs.
When compared to SMAs and PZTs, SMPs have the following advantages: SMP materials have better
elastic deformation retention, are less expensive, have a tuneable stiffness, can work over a wide
temperature range, and are easier to produce. However, among of the key disadvantages of SMPs include
their low modulus, which leads in modest recovery stresses/forces, their response time, and the minimal
number of cycles that can be achieved.
Temperature has long been the most common activation stimulus, although others include light,
magnetic or electric fields, irradiation, and pH changes.
• Nanocomposites manufactured by 3D Printing

Because of their high specific strength and specific modulus, continuous fiber reinforced
polymer composites offer a lot of potential.
Due of their high strength and light weight, carbon fiber reinforced polymers (CFRP) have
shown significant promise. Free-form shape design and one-piece molding are limited in traditional
CFRP manufacturing methods. 3D printing, on the other hand, has advantages in the construction of
complicated components, the elimination of assembly activities, and precise entity duplication.
Fused filament fabrication (FFF), powder bed and inkjet head 3D printing (3DP), stereolithography
(SLA), and selective laser sintering are all examples of 3D printing technologies (SLS).
The FFF process, for example, permits parts to be manufactured by depositing tiny lines side by
side and layer by layer, which is ideal for printing continuous fiber filaments. Towpreg extrusion, in-situ
impregnation, and co-extrusion with towpreg are the three types of FFF printers for CFRP.
Due to the lack of compaction during printing procedures along the construction direction,
adhesions between deposited lines and between layers in 3D printed components are known to be weaker
than those made using traditional methods.
As a result, the fundamental shortcoming of 3D printing technology is recognized as inadequate
interfacial adhesion, which causes premature sample failure. As a result, more research is needed into
ways to prevent vacuum formation during printing and assure adequate interfacial bonding.
Mechanical qualities and application possibilities of 3D printed CFRP are influenced by interfacial
quality.
Technologies and Processes at the Nanoscale (TPNE)

References
[1] B.Fiedler; F.H.Gojny; M.H.G.Wichmann; Mathias C.M.; K.Schulte; “Fundamental aspects of nano-reinforced
composites”, Composites Science and Technology, Volume 66, Issue 16, 18 December 2006, Pages 3115-3125,
ELSEVIER
[2] S.Kanagaraj; F.R.Varanda; T.V.Zhil’tsova; M.S.A.Oliveira; J.A.O.Simões; “Mechanical properties of high
density polyethylene/carbon nanotube composites”, Composites Science and Technology, Volume 67, Issue 15-16,
December 2007, Pages 3071-3077, ELSEVIER
[3] M.A.Fonseca; B.Abreu; F.A.M.M.Gonçalves; A.G.M.Ferreira; R.A.S.Moreira; M.S.A.Oliveira; “Shape memory
polyurethanes reinforced with carbon nanotubes”, Composites Science and Technology, Volume 99, May 2013,
Pages 105-111, ELSEVIER
[4] Y.Wu; K.Wang; V.Neto; Y.Peng; R.Valente; S.Ahzi; “Interfacial behaviours of continuous carbon fiber
reinforced polymers manufactured by fused filament fabrication: A review and prospect”, International Journal of
Material Forming, Volume 15, Article number: 18 (2022)