Tensile and impact properties of carbon filled nylon‐6,6 based resins

Electrically and thermally conductive resins can be produced by adding conductive fillers to insulating polymers. Mechanical properties such as tensile modulus, ultimate tensile stress, strain at ultimate tensile stress, and notched Izod impact strength are also important and cannot be ignored. This study focused on performing compounding runs, followed by injection molding and evaluation of tensile and impact properties of carbon filled nylon‐6,6 based resins. The three carbon fillers investigated include an electrically conductive carbon black, synthetic graphite particles, and a surface treated polyacrylonitrile (PAN) based carbon fiber. Resins containing varying amounts of these single carbon fillers were produced and tested. In addition, combinations of fillers were investigated by conducting a full 2³ factorial design and a complete replicate. The addition of carbon fiber increased the composite tensile modulus, ultimate tensile stress, and impact strength. Also, in many cases, combining two or three different fillers caused a statistically significant effect at a 95% confidence level. When comparing the results of this study with prior work, it appears that increased heteroatoms present on the carbon fiber surface likely improve composite ultimate tensile stress and impact strength. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2881–2893, 2004     

Thermally conductive nylon 6,6 and polycarbonate based resins. II. Modeling

Increasing the thermal conductivity of typically insulating polymers opens new markets. A thermally conductive resin can be used for heat‐sink applications. This research focused on extruding followed by injection molding and thermal conductivity testing of carbon filled nylon 6,6 and polycarbonate‐based resins. The three carbon fillers investigated included an electrically conductive carbon black, synthetic graphite particles, and a milled pitch‐based carbon fiber. For each polymer, conductive resins were produced and tested that contained varying amounts of these single carbon fillers. In addition, combinations of fillers were investigated by conducting a full 2³ factorial design and a complete replicate in each polymer. These through‐plane thermal conductivity experimental results were then compared to results predicted by several different thermal conductivity models. An improved thermal conductivity model was developed that fit the experimental results well for resins that contained single fillers and combinations of different fillers. This improved model was based on the original Nielsen model. A single value for the shape parameter, A (which is needed in Nielsen's model), was used for all three different fillers. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 123–130, 2003     

Thermally conductive nylon 6,6 and polycarbonate based resins. I. Synergistic effects of carbon fillers

Increasing the thermal conductivity of typically insulating polymers, such as nylon 6,6, opens new markets. A thermally conductive resin can be used for heat‐sink applications. This research focused on performing compounding runs followed by injection molding and thermal conductivity testing of carbon filled nylon 6,6 and polycarbonate based resins. The three carbon fillers investigated included an electrically conductive carbon black, synthetic graphite particles, and a milled pitch‐based carbon fiber. For each polymer, conductive resins were produced and tested that contained varying amounts of these single carbon fillers. In addition, combinations of fillers were investigated by conducting a full 2³ factorial design and a complete replicate in each polymer. The objective of this article was to determine the effects and interactions of each filler on the thermal conductivity properties of the conductive resins. From the through‐plane thermal conductivity results, it was determined that for both nylon 6,6 and polycarbonate based resins, synthetic graphite particles caused the largest increase in composite thermal conductivity, followed by carbon fibers. The combination of synthetic graphite particles and carbon fiber had the third most important effect on composite thermal conductivity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 112–122, 2003     

Comparison of the guarded‐heat‐flow and transient‐plane‐source methods for carbon‐filled nylon 6,6 composites: Experiments and modeling

In this study, two different carbons (synthetic graphite particles and carbon fiber) were added to nylon 6,6, and the resulting composites were tested for thermal conductivity. The first goal of this work was to compare through‐plane thermal conductivity results from the guarded‐heat‐flow method and the transient‐plane‐source method. The results showed that both test methods gave similar through‐plane thermal conductivity results for composites containing 10–40 wt % synthetic graphite and for composites containing 5–40 wt % carbon fiber. The advantages of using the transient‐plane‐source method were that the in‐plane thermal conductivity was also measured and the experimental time was shorter than that of the guarded‐heat‐flow method. The second goal of this work was to develop and use a detailed finite‐element analysis to model heat transfer within a carbon‐filled nylon 6,6 composite sample for the transient‐plane‐source method and compare these results to actual experimental results. The results showed that the finite‐element model compared well with the actual experimental data. The finite‐element model could be used in the future as a design tool to predict the dynamic thermal response of different composite materials for many applications. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Shielding‐effectiveness modeling of carbon‐fiber/nylon‐6,6 composites

We have formulated a linear theory for the shielding effectiveness of composite matrix materials and have tested the theory for various amounts of ThermalGraph DKD X carbon fiber within nylon 6,6. The theory predicts that the most important parameters for the shielding effectiveness of a sample are the carbon‐fiber volume percentage and the frequency of the wave to be shielded. Although we expected the model to be valid at low filler‐loading levels, it actually performs remarkably, covering an electrical‐resistivity range of 10¹⁶ (at low filler‐loading levels) to 10¹ Ω cm (at high filler‐loading levels), well above the percolation threshold of electrical‐resistivity theory. The model performs much better than those reported in the literature and can be used to determine filler loadings needed to provide a certain level of shielding of electromagnetic waves. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 62–69, 2005     

Electrical conductivity of carbon‐filled polypropylene‐based resins

Adding conductive carbon fillers to insulating thermoplastic resins increases composite electrical conductivity. Often, as much of a single type of carbon filler is added to achieve the desired conductivity and still allow the material to be molded into a bipolar plate for a fuel cell. In this study, various amounts of three different carbons (carbon black, synthetic graphite particles, and carbon nanotubes) were added to polypropylene resin. The resulting single‐filler composites were tested for electrical resistivity (1/electrical conductivity). The effects of single fillers and combinations of the different carbon fillers were studied via a factorial design. The percolation threshold was 1.4 vol % for the composites containing only carbon black, 2.1 vol % for those containing only carbon nanotubes, and 13 vol % for those containing only synthetic graphite particles. The factorial results indicate that the composites containing only single fillers (synthetic graphite followed closely by carbon nanotubes and then carbon black) caused a statistically significant decrease in composite electrical resistivity. All of the composites containing combinations of different fillers had a statistically significant effect that increased the electrical resistivity. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Tensile modulus modeling of carbon‐filled liquid crystal polymer composites

Electrically and thermally conductive resins can be produced by adding conductive fillers to insulating polymers. Mechanical properties, such as tensile modulus, are also important. This research focused on performing compounding runs followed by injection molding and tensile testing of carbon‐filled Vectra liquid crystal polymer. The two carbon fillers investigated were Thermocarb synthetic graphite particles and Fortafil carbon fiber at varying filler amounts. The tensile modulus experimental results were compared to results predicted by several different models. It was found that the Halpin Tsai 2D Randomly Oriented fiber model provided the best fit to the experimental data. The degree of filler‐polymer adhesion was also studied with nanoscratch tests for synthetic graphite and carbon fiber fillers in three polymers: Vectra, nylon 6,6, and polycarbonate. The adhesion trends seen in the nanoscratch tests showed qualitative agreement with the tensile modulus, and should be considered in formulating advanced tensile modulus models. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Electrical conductivity modeling of carbon‐filled liquid‐crystalline polymer composites

Electrically conductive resins are needed for bipolar plates used in fuel cells. Currently, the materials for these bipolar plates often contain a single type of graphite powder in a thermosetting resin. In this study, various amounts of two different types of carbon, carbon black and synthetic graphite, were added to a thermoplastic matrix. The resulting single‐filler composites were tested for electrical conductivity, and electrical conductivity models were developed. Two different models, the Mamunya and additive electrical conductivity models, were used for both material systems. It was determined how to modify these models to reduce the number of adjustable parameters. The models agreed very well with experimental data covering a large range of filler volume fractions (from 0 to 12 vol % for the carbon black filled composites and from 0 to 65 vol % for the synthetic graphite filled composites) and electrical conductivities (from 4.6 × 10^?17 S/cm for the pure polymer to 0.5 S/cm for the carbon black filled composites and to 12 S/cm for the synthetic graphite filled composites). © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3293–3300, 2006     

Development of an additive equation for predicting the electrical conductivity of carbon‐filled composites

The electrical conductivity of polymeric materials can be increased by the addition of carbon fillers. The resulting composites can be used in applications such as electrostatic dissipation and interference shielding. Electrical conductivity models are often proposed to predict the conductivity behavior of these materials. The electrical conductivity of carbon‐filled polymers was studied here by the addition of three single fillers to nylon 6,6 and polycarbonate in increasing concentrations. The fillers used in this project were carbon black, synthetic‐graphite particles, and milled pitch‐based carbon fibers. Materials were extruded and injection‐molded into test specimens, and then the electrical conductivity was measured. Additional material characterization tests included optical microscopy for determining the filler aspect ratio and orientation. The filler and matrix surface energies were also determined. An updated model developed by Mamunya and others and a new additive model (including the constituent conductivities, filler volume fraction, percolation threshold, constituent surface energies, filler aspect ratio, and filler orientation) fit the electrical conductivity results well. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2280–2299, 2003     

Nanoscratch testing to assess the fiber adhesion of short‐carbon‐fiber composites

In a composite material, the degree of adhesion between the fiber and the matrix plays an important role in the overall performance of the material. Because the load between the fiber and the matrix is realized throughout the interphase region material, a lot of effort has gone into characterizing the strength of the interphase. In this study, nanoscratch tests on the composite samples were used to provide a relative measure of adhesion in different composite materials. Carbon‐filled nylon 6,6 and polycarbonate resins were evaluated with this method. The carbon fillers we used were polyacrylonitrile‐based carbon fibers sized and surface‐treated for the respective matrix and pitch‐based carbon fibers without any sizing or surface treatment. Tensile and X‐ray photoelectron spectroscopy data for the composites we considered are also presented to compare to the nanoscratch results. It is shown that nanoscratch testing on the composites, with the proposed data analysis, can be an effective tool for determining the relative degree of adhesion between different composites. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 328–335, 2007     

Measuring and predicting in‐plane thermal conductivity of carbon‐filled nylon 6,6 polymer composites

In this study, two different carbons (synthetic graphite particles and carbon fiber) were added to nylon 6,6, and the resulting composites were tested for both the through‐plane thermal conductivity k_thru and the in‐plane thermal conductivity k_in, using the transient plane source method. The first goal of this work was to use a finite element model to develop a procedure to accurately measure the material properties using this relatively new analytical procedure. Reproducible data can be obtained for nylon 6,6 polymer composites, by choosing a power dissipation (an input parameter to the transient plane source method) corresponding to a sensor temperature increase of 2 K above the initial temperature after 5 s. The second goal of this work was to develop a simple empirical model for the in‐plane thermal conductivity, which is easily measured with the transient plane source method. The results show that the product of the through‐plane and in‐plane thermal conductivities is a linear function of the volume percent ϕ. As the through‐plane thermal conductivity of these composites is accurately predicted with a modified Nielsen model, this empirical relationship can be used to estimate in‐plane thermal conductivities for a range of applications. POLYM. COMPOS. 27:1–7, 2006. © 2005 Society of Plastics Engineers     

Shielding effectiveness of carbon‐filled polycarbonate composites

In this project, varying amounts of three different carbons [carbon black (CB), carbon nanotubes (CNT), and graphene nanoplatelets (GNP)] were added to polycarbonate (PC). The resulting single filler composites were tested for shielding effectiveness (SE). The effects of single fillers and combinations of two different carbon fillers were studied via a factorial design. At the highest single filler loadings, the following SE results were obtained at 800 MHz: 18.9 dB for 10 wt % CB/PC, 18.4 dB for 8 wt % CNT/PC, and 6.3 dB for 15 wt % GNP/PC. The highest SE value of 21.4 dB was measured for the 5 wt % CB/5 wt % CNT/PC composite and could be used in SE applications (typically > 20 dB is needed). Statistically significant equations were developed that could be used to predict the SE of composites containing these fillers. In addition, it was determined that the composite SE is higher than what would be expected from the additive effect of each single filler for the CB/GNP/PC composites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42719.     

In‐plane thermal conductivity modeling of carbon‐filled liquid crystal polymer–based resins

Adding conductive carbon fillers to insulating thermoplastic resins increases composite electrical and thermal conductivity. In this study, varying amounts of three different carbons (carbon black, synthetic graphite particles, and carbon fiber) were added to Vectra A950RX liquid crystal polymer. The in‐plane thermal conductivity of the resulting single filler composites was tested. The results showed that adding synthetic graphite particles caused the largest increase in the in‐plane thermal conductivity of the composite. The composites were modeled using ellipsoidal inclusion problems to predict the effective in‐plane thermal conductivities at varying volume fractions with only physical property data of the constituents. The synthetic graphite and carbon black were modeled using the average field approximation with ellipsoidal inclusions and the model showed good agreement with the experimental data. The carbon fiber polymer composite was modeled using an assemblage of coated ellipsoids and the model showed good agreement with the experimental data. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Simulation of continuous solid‐phase polymerization of nylon 6,6. III. Simplified model

Solid‐phase polymerization (SPP) reactors are used to increase the degree of polymerization (DP) during nylon 6,6 production. In previous articles, a reactor model with partial differential equations (PDEs) in time and two spatial dimensions was developed to describe dynamic changes in polymer property profiles (DP, temperature, and moisture content) over the height of the reactor and within the polymer particles. In the current article, a simplified model is developed by deriving appropriate expressions for heat‐ and mass‐transfer coefficients and performing a lumped heat‐ and mass‐transfer analysis. Using this approach, the radial dimension is removed from the PDEs, so that the effort required to solve the model equations is substantially reduced. Predictions of the complex and simplified models are compared through simulation of two different start‐up processes. Good agreement between simplified and complex models is obtained, indicating that the simplified model can be used in place of the complex model if the polymer properties profiles within individual particles are not of particular concern to the model user. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3701–3712, 2003     

Electrical conductivity and rheology of carbon‐filled liquid crystal polymer composites

One emerging market for electrically conductive resins is for bipolar plates for use in fuel cells. Adding carbon fillers to thermoplastic resins increases composite electrical conductivity and viscosity. Current technology often adds as much of a single type of carbon filler as possible to achieve the desired conductivity, while still allowing the carbon‐filled thermoplastic matrix material to be extruded and molded into a bipolar plate. In this study, varying amounts of two different types of carbon, one carbon black and one synthetic graphite, were added to Vectra A950RX liquid crystal polymer. The resulting single filler composites were then tested for electrical conductivity and rheological properties. The electrical conductivity followed that typically seen in polymer composites with a percolation threshold at 4 vol % for carbon black and at 15 vol % for synthetic graphite. Over the range of shear rates studied, the viscosity followed a shear‐thinning power law model with power‐law exponent (n ? 1) = ?0.5 for neat Vectra A950RX and (n ? 1) = ?0.7 for highly filled composite materials. Viscosity increased with increasing filler volume fraction for all shear rates. The viscosity–enhancement effect was more rapid for the composites containing carbon black when compared with those containing synthetic graphite. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2680–2688, 2006     

Conducting polymer composites of zinc‐filled nylon 6

The present work is concerned with the effect of processing variables and filler concentration on the electrical conductivity, hardness, and density of composite materials prepared by compression molding of a mixture of zinc powder and nylon 6 powder. The electrical conductivity of the composites is <10^?12 S/cm, unless the metal content reaches the percolation threshold at a volume fraction of about 0.18, beyond which the conductivity increases markedly by as much as 10 orders of magnitude. The density of the composites was measured and compared with values calculated by assuming different void levels within the samples. Furthermore, it is shown that the hardness increases with the increase of metal concentration, but for values of filler volume fraction higher than about 0.30 the hardness of samples remains almost constant. Two parameters of molding process, temperature and time, were shown to have a notable effect on the conductivity of composites, whereas pressure has no influence on this property in the pressure range considered. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1449–1454, 2001     

Effects of carbon fillers on tensile and flexural properties in polypropylene‐based resins

A potential application for conductive resins is in bipolar plates for use in fuel cells. The addition of carbon filler can increase the electrical and thermal conductivities of the polymer matrix but will also have an effect on the tensile and flexural properties, important for bipolar plates. In this research, three different types of carbon (carbon black, synthetic graphite, and carbon nanotubes) were added to polypropylene and the effects of these single fillers on the flexural and tensile properties were measured. All three carbon fillers caused an increase in the tensile and flexural modulus of the composite. The ultimate tensile and flexural strengths decreased with the addition of carbon black and synthetic graphite, but increased for carbon nanotubes/polypropylene composites due to the difference in the aspect ratio of this filler compared to carbon black and synthetic graphite. Finally, it was found that the Nielsen model gave the best prediction of the tensile modulus for the polypropylene based composites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Determination of moisture content in nylon 6,6 by near‐infrared spectroscopy and chemometrics

The effects of moisture on the morphology and mechanical properties of polyamides have been extensively studied by a number of researchers. However, the assessment of water content in the resins has been carried out by thermal or thermogravimetric methods, which are destructive. In the present work partial least‐squares (PLS) calibration models based on near‐infrared (NIR) spectroscopy were produced in order to predict the moisture content of nylon 6,6. Differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and the loss‐on‐drying (LOD) method were used as reference methods. TGA, LOD, DSC, and NIR analysis were performed in parallel, and the obtained data were used for multivariate calibration purposes. Data pretreatment techniques such as derivation and multiplicative scattering correction (MSC) successfully eliminated the baseline offset present in the raw spectra and compensated for differences in thickness and light scattering of the analyzed samples. Calibration models were validated by full cross validation with the help of a test set. A comparison of the prediction ability of PLS models based on pretreated data was also done. NIR spectroscopy is a rapid and nondestructive method for the determination of moisture in recycled nylon. The moisture content can be predicted with a RMSEP = 0.05 wt %. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 2165–2170, 2003     

Effects of carbon fillers on the rheology of highly filled liquid‐crystal polymer based resins

Adding conductive carbon fillers to insulating resins increases the composite electrical and thermal conductivity. Often, enough of a single type of carbon filler is added to achieve the desired conductivity while still allowing the material to be molded into a bipolar plate for a fuel cell. In this study, various amounts of three different carbons (carbon black, synthetic graphite particles, and carbon fiber) were added to Vectra A950RX liquid‐crystal polymer. The rheological properties of the resulting single‐filler composites were measured. In addition, the rheological properties of composites containing combinations of different carbon fillers were studied via a factorial design. In all cases, the viscosity increased with increasing filler volume fraction and followed a shear‐thinning power‐law model. The factorial design results indicated that each of the single fillers and all the filler combinations caused a statistically significant increase in the composite viscosity when compared at a shear rate of 500 s^?1 or at a stress of 10⁵ Pa. For composites containing synthetic graphite particles and/or carbon fiber, the viscosity variation with the volume fraction of carbon followed a modified Maron–Pierce equation. When compared at a constant volume fraction of carbon, composites containing carbon black showed viscosity enhancement above and beyond that shown by the other composites. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Structure and properties of polyimide‐g‐nylon 6 and nylon 6‐b‐polyimide‐b‐nylon 6 copolymers

Polyimide‐g‐nylon 6 copolymers were prepared by the polymerization of phenyl 3,5‐diaminobenzoate with several diamines and dianhydrides with a one‐step method. The polyimides containing pendant ester moieties were then used as activators for the anionic polymerization of molten ε‐caprolactam. Nylon 6‐b‐polyimide‐b‐nylon 6 copolymers were prepared by the use of phenyl 4‐aminobenzoate as an end‐capping agent in the preparation of a series of imide oligomers. The oligomers were then used to activate the anionic polymerization of ε‐caprolactam. In both the graft and copolymer syntheses, the phenyl ester groups reacted quickly with caprolactam anions at 120°C to generate N‐acyllactam moieties, which activated the anionic polymerization. All the block copolymers had higher moduli and tensile strengths than those of nylon 6. However, their elongations at break were much lower. The graft copolymers based on 2,2′‐bis[4‐(3,4‐dicarboxyphenoxy)phenyl]propane dianhydride and 2,2′‐bis[4‐(4‐aminophenoxy)phenyl]propane displayed elongations comparable to that of nylon 6 and the highest moduli and tensile strengths of all the copolymers. The thermal stability, moisture resistance, and impact strength were dramatically increased by the incorporation of only 5 wt % polyimide into both the graft and block copolymers. The graft and block copolymers also exhibited improved melt processability. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 300–308, 2006