Latex technology is a unique and scalable process whereby polymeric nano‐ and microcomposites can be prepared. The use of water as a processing media and minimal energy requirements make the process environmentally friendly. Furthermore, the process is applicable to various fillers and polymers. In this article, special attention is paid to various analytical methods with which the process can be monitored and assessed, as well as to strategies to optimize the final composites properties. Focus is placed on conductive nanocomposites prepared using carbon nanotubes and the latex technology process. A brief introduction to the percolation theory of rod‐like fillers is given; the influence that the filler and matrix properties have on this theory and the simulated conductive behavior are also addressed. Methods to manipulate the final composite properties through the clever use of chemical and physical adjustments are described. Finally, applications of materials prepared using latex technology are also discussed.

Graphene was produced from graphite powder using the three best known water-based conversion approaches. The first two are based on chemical oxidation methods, only differing in the reduction process, either by the use of hydrazine or by thermal expansion, respectively. The third one is based on long-term ultrasonic exfoliation. Water/surfactant solutions were prepared with these three nanofillers and latex technology concept was applied for the preparation of conductive graphene/polystyrene composites with well-dispersed graphene platelets. The samples were characterized with respect to filler properties and morphology, and their influences on electrical conductive properties of the composites were compared. Microscopic studies showed that both reduction processes lead to agglomeration/wrinkling of the platelets, even though they yield composites with high conductivity and low percolation threshold. Although mechanical ultrasound exfoliation of graphite produces less defective multi-layer graphene, these platelets have a smaller lateral size and their composites exhibit a higher percolation threshold. Differences in electronic transport behavior were observed, which suggest direct contact transport competing with tunneling. (C) 2015 Elsevier Ltd. All rights reserved.

The effect of the dispersed state of graphene is studied as a factor influencing the electrical percolation threshold of graphene/polystyrene nanocomposites. We find the percolation threshold of our nanocomposites, prepared with graphene dispersions with different thermodynamic stabilities, degrees of exfoliation, and size polydispersities, to range from 2 to 4.5 wt %. Connectedness percolation theory is applied to calculate percolation thresholds of the corresponding nanocomposites, based on the premise that size polydispersity of graphene platelets in the corresponding solutions must have a strong influence on it. Theory and experimental results agree qualitatively.

The electrical conductivity of graphene, multi-wall carbon nanotubes, carbon black nanopowders and graphite powder is characterized using paper-like films and by means of powder compression. The large difference in surface area of these materials results in different packing density and number of contact spots, influencing the macroscopic conductivity of the compacts during powder compression. The results are compared with the percolation threshold and final conductivity of polypropylene (PP) composites, using latex technology for the incorporation of the carbon fillers in the polymer. Even though the PP composites produced in this work exhibit percolation thresholds as low as 0.3wt.%, the final conductivity for all the composites is below 1.5S/m. Reasons why the high value of ∼103S/m, which is obtained for graphene- and nanotube-based paper films or graphite compacts, is not reached for the composites are investigated.

The creation of conducting networks within composite materials is very important to reduce the generally expensive conducting polymer content, to create conducting/nonconducting domains, and to adjust conductivity of the final composite. We developed cellulose/poly(3,4-ethylenedioxythiophene)/poly(styrene sulfonate) (PEDOT:PSS)-based polystyrene (PS) composites with an extremely low percolation threshold of the conductive polymer. The percolation threshold of PEDOT:PSS in PEDOT:PSS/PS blends, being 2.2 wt % (2.31 vol%), was lowered to 0.4 wt % (0.42 vol%) by adding 0.8 wt % (0.56 vol%) of cheap, nonconducting cellulose nanowhiskers. Such a low percolation threshold of PEDOT:PSS is attributed to the templating effect of the cellulose nanowhiskers: the conducting PEDOT:PSS is thought to adsorb onto the cellulose surface and by doing that (at least partly) covers the network formed by the percolating, high aspect ratio cellulose whiskers in the PS matrix. UV-vis experiments indeed point to an interaction between PEDOT:PSS and the cellulose whiskers, confirming the templating of PEDOT:PSS onto the nanowhiskers during processing and film formation. This approach can be applied to other conducting composites to reduce the required conducting polymer content and increase the ease of processing as electrical percolation is directly achieved.

The concept of liquid-phase dispersion was applied for the preparation of well-dispersed suspensions of MWCNTs and graphene in chloroform, using long-time ultra-sonication without the use of surfactants. The dispersions with pre-defined filler concentration (0.5mg/ml) were monitored via UV–Vis until the achievement of optimum exfoliation (6h). PS/PPO polymer was dissolved in chloroform and graphene- and MWCNTs-based composite tablets were prepared via solution blending, subsequent drying and hot pressing. The well-dispersed organization of the fillers inside the polymer matrix, visualized with scanning electron microscopy, resulted in ultimate conductivities and percolation thresholds of 57S/m and 0.2wt.% for nanotubes composites, and 0.9S/m and ∼1wt.% for graphene composites, respectively. Dynamic mechanical analysis showed that an increase in the storage moduli of the PS/PPO matrix could be gradually obtained by the insertion of fillers, e.g. reaching ∼30% of enhancement by the addition of 3wt.% of graphene filler. The same trend in improvement, at lower augmentation, was observed for the corresponding nanotubes-based composites.

A latex technique is used to prepare graphene/polystyrene and graphene/poly(propylene) composites with varying GR loadings. Their electrical properties and the corresponding volume organisation of GR networks are studied. Percolation thresholds for conduction are found to be about 0.9 and 0.4 wt% for GR/PS and GR/PP with maximum obtained conductivities of 12 and 0.4 S m -1 for GR loadings of 2 wt%, respectively. Investigations using SEM and electrical conductivity measurements show that for the preparation conditions used GR forms an isotropic 3D network in the PS matrix, but GR forms a 2D network in the PP matrix. The different GR network organisations are possibly forced by the different melt flow behaviour of the matrix polymers during processing and the subsequent crystallisation of PP.

The local electrical properties of a conductive graphene/polystyrene (PS) composite sample are studied by scanning probe microscopy (SPM) applying various methods for electrical properties investigation. We show that the conductive graphene network can be separated from electrically isolated graphene sheets (GS) by analyzing the same area with electrostatic force microscopy (EFM) and conductive atomic force microscopy (C-AFM). EFM is able to detect the graphene sheets below the sample surface with the maximal depth of graphene detection up to approximate to 100 nm for a tip-sample potential difference of 3 V. To evaluate depth sensing capability of EFM, the novel technique based on a combination of SPM and microtomy is utilized. Such a technique provides 3D data of the GS distribution in the polymer matrix with z-resolution on the order of approximate to 10 nm. Finally, we introduce a new method for data correction for more precise 3D reconstruction, which takes into account the height variations.

Single graphene sheets, a few graphene layers, and bulk graphite, obtained via both micromechanical cleavage of highly oriented pyrolytic graphite and carbon vapor deposition methods, were deposited on a thin glass substrate without the use of any chemical treatment. Micro-Raman spectroscopy, tip-enhanced Raman spectroscopy (TERS), and tip-enhanced Raman spectroscopy mapping (TERM) were used for characterization of the graphene layers. In particular, TERM allows for the investigation of individual graphene sheets with high Raman signal enhancement factors and allows for imaging of local defects with nanometer resolution. Enhancement up to 560% of the graphene Raman band intensity was obtained using TERS. TERM (with resolution better than 100 nm) showed an increase in the number of structural defects (D band) on the edges of both graphene and graphite regions.

Graphene was produced from graphite powder using the three best known water-based conversion approaches. The first two are based on chemical oxidation methods, only differing in the reduction process, either by the use of hydrazine or by thermal expansion, respectively. The third one is based on long-term ultrasonic exfoliation. Water/surfactant solutions were prepared with these three nanofillers and latex technology was applied for the preparation of conductive graphene/polystyrene composites, with well-dispersed graphene platelets. Microscopic studies showed that both reduction processes lead to agglomeration/wrinkling of the nanoplatelets, even though they yield composites with high conductivity and low percolation threshold. Although mechanical ultrasound exfoliation of graphite produces less defective multi-layer graphene, these platelets have a smaller lateral size and their composites exhibit a higher percolation threshold.

The electrical conductivity of different carbon materials (multi-walled carbon nanotubes, graphene, carbon black and graphite), widely used as fillers in polymeric matrices, was studied using compacts produced by a paper preparation process and by powder compression. Powder pressing assays show that the bulk conductivity depends not only on the intrinsic material properties but is also strongly affected by the number of particle contacts and the packing density. Conductivities at high pressure (5MPa) for the graphene, nanotube and carbon black show lower values (~102S/m) as compared to graphite (~103S/m). For nanotube, graphene and graphite particles, the conductive behavior during compaction is governed by mechanical particle arrangement/deformation mechanisms while for carbon black this behavior is mainly governed by the increasing particle contact area. The materials resulting from the paper preparation process for carbon black and graphite showed similar conductivity values as for the compacts, indicating a limited effect of the surfactant on the conductivity. The paper preparation process for the large surface area nanotube and graphene particles induces a highly preferred in-plane orientation, thereby yielding largely the single particle intrinsic conductivity for the in-plane direction, with values in the order of 103S/m.

Applications of composites based on carbon nanotubes and graphene require their exfoliation and dispersion in a polymer matrix. One of the main approaches to disperse and exfoliate carbon nanotubes and graphene is based on the use of surfactants. Here we review the surfactants utilized for dispersing carbon nanotubes and graphene, the mechanisms of filler stabilization and the methods for composite preparation based on the use of surfactants to get conductive polymer composites with minimum nanofiller loading.

The latex technology concept is applied for the preparation of graphene/polystyrene nanocomposites. Aqueous dispersions of graphene are obtained viaoxidation and exfoliation of graphite and subsequent reduction in the presence of surfactant. The quality of the prepared nanofillers is characterized by atomic force microscopy (AFM). Different amounts of aqueous graphene dispersions are then mixed with polystyrene (PS) latex and composites are prepared by freeze-drying and subsequent compression molding. The final bulk and local conductivities of the composites are respectively measured by a four-point method and by means of conductive AFM (C-AFM) analysis. The morphology of the conductive nanocomposites is studied with charge contrast scanning electron microscopy imaging (SEM). The percolation threshold for conduction is below 1 wt% of graphene in the composites, and a maximum conductivity of about 15 S m−1 can be achieved for 1.6–2 wt% nanofiller.