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Synergistic Effects of Carbon Fillers on Shielding Effectiveness in Conductive Nylon 6,6- and Polycarbonate-Based Resins
Synergistic Effects of Carbon Fillers on Shielding Effectiveness in Conductive Nylon 6,6- and Polycarbonate-Based Resins

Synergistic Effects of Carbon Fillers on Shielding Effectiveness in Conductive Nylon 6,6- and Polycarbonate-Based Resins

QUINTON J. KRUEGER, JULIA A. KING

Department of Chemical Engineering, Michigan Technological University, Houghton, Michigan 49931-1295

Received: May 29, 2002 Accepted: January 9, 2003

ABSTRACT:

Electrically conductive resins can be made by adding electrically

conductive fillers to typically insulating polymers. Resins with an electrical resistivity of approximately 10 0 cm or less can be used for electromagnetic and radio frequency interference shielding applications. This research focused on performing compounding runs followed by injection molding and shielding effectiveness (SE) 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 2 3 factorial design and a complete replicate in each polymer. The objective of this study was to determine the effects and interactions of each filler on the SE properties of the conductive resins. Carbon

Correspondence to: Julia A. King; e-mail: jaking@mtu.edu. Contract grant sponsor: National Science Foundation. Contract grant number: DMI-9973278.

Advances in Polymer Technology, Vol. 22, No. 2, 96–111 (2003)

C

2003 Wiley Periodicals, Inc.

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

black caused the largest increase in SE. Also, each single ller and each two ller interaction caused a statistically signicant increase in SE. C 2003 Wiley Periodicals, Inc. Adv Polym Techn 22: 96111, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.10040

KEY WORDS:

Composites, Fillers, Nylon, Polycarbonates, Shielding

Introduction

M ost polymer resins are electrically insulating. Increasing the electrical conductivity of these

resins allows them to be used in other applications. An electrically conductive resin can be used for static dissipative, semiconductive (e.g., fuel gages), and electromagnetic interference (EMI)/radio frequency interference (RFI) shielding applications (e.g., com- puter and cellular phone housings). The advantages of conductive resins as compared to metals (typi- cally used) include improved corrosion resistance, lighter weight, and the ability to adapt the conduc- tivity properties to suit the application needs. Electrical resistivity (1/electrical conductivity) values for various materials are typically in the range from 10 14 to 10 17 for polymers, 10 2 for carbon black, 10 4 for highly graphitized pitch-based carbon ber, 10 5 for high purity synthetic graphite, and 10 6 for metals such as aluminum and copper (all val- ues in cm). One approach to improving the elec- trical conductivity of a polymer is through the addi- tion of a conductive ller material, such as carbon and metal. 1,2 Conductive resins with an electrical resistivity (ER) ranging from approximately 10 10 to 10 3 cm can be used for static dissipative applica- tions. Conductive resins with ER ranging from ap- proximately 10 2 to 10 1 cm can be used for semicon- ductive applications. Those with ER approximately 10 0 cm or less can be used for EMI/RFI shielding applications. 3 EMI is electrical energy, either in the electromag- netic or in the radio frequency range, that is emitted by computer circuits, radio transmitters, uorescent lamps, electric motors, overhead power lines, light- ning, etc. EMI/RFI can interfere with the operation of other electronic equipment near it, such as caus- ing the unwanted operation of garage door openers, corrupting data in computer systems, and causing pacemakers to malfunction. Federal Communica- tions Commission regulations control the amount of energy that can be emitted by an electronic product. The need for EMI/RFI materials is growing because

of more stringent regulation on electronic noise, as well as the increased need for smaller, more densely packed electronic components. A shielding material is typically used to encase an electronic product to prevent the enclosed product from emitting electro- magnetic or radio frequency energy. The shielding material either absorbs or reects the energy within the material. 4 The shielding effectiveness (SE) of a material is the ratio of the power received with and without a material present for the same incident power. It is expressed in units of decibels (dB), as shown in Eq. (1). 5

SE = 10 log(P 1 /P 2 )

(1)

where P 1 is the received power with the material present and P 2 is the received power without the ma- terial present. For EMI/RFI shielding applications, typically a SE of at least 20 dB (indicates that 99% of the electromagnetic (EM) energy is reected or ab- sorbed by the material) is needed. 6 A SE of 30 dB indicates that 99.9% of the EM energy is reected or absorbed by the material, with only 0.1% exiting the shielding material. There are many studies concerning adding a vary- ing amount of a single conductive ller to a polymer matrix so as to produce an electrically conductive, shielding material. For example, carbon black, car- bon bers, stainless steel bers, and nickel-coated carbon bers have been used. 6,7 Bushko, Stokes, and Wilson showed that a conductive resin containing 24 wt % carbon ber in polycarbonate provided a SE of 35 dB at a frequency of 100 MHz. 6 Bigg showed that adding 11 vol % carbon black to polypropy- lene produced a material with a SE of 20 dB at 100 MHz. 8 Versiek reported that for polycarbonate- based resins, adding 2.5 and 6.0 wt % stainless steel (302 alloy) bers resulted in SE values of 30 and 40 dB, respectively. 9 Murthy reported a SE of ap- proximately 35 dB at 1000 MHz for a conductive resin containing 10 wt % nickel-coated carbon ber in polycarbonate. 10 In this work, researchers performed compound- ing runs followed by injection molding and SE

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

testing of carbon-lled resins. Two different poly- mers were used: nylon 6,6 and polycarbonate. The three carbon llers investigated included an elec- trically conductive carbon black, synthetic graphite particles, and a milled pitch-based carbon ber. For each polymer, 14 formulations that contained vary- ing amounts of these single carbon llers were pro- duced and tested. In addition, combinations of llers were investigated by conducting a full 2 3 factorial de- sign and a complete replicate in each polymer. The goal of this project was to determine the effects and interactions of each ller on the SE properties of the conductive resins.

fi ller on the SE properties of the conductive resins. Materials and Experimental Methods MATERIALS Two

Materials and Experimental Methods

MATERIALS

Two matrix materials were utilized in this project. The rst matrix used was DuPont Zytel 101 NC010, an unmodied semicrystalline nylon 6,6 polymer. The second matrix used was Lexan HF 1110-111N, which is an amorphous engineering thermoplastic produced by GE Plastics. The properties of these polymers are discussed elsewhere. 1113 Three different carbon llers were employed in this project. Akzo Nobel Ketjenblack EC-600 JD, an electrically conductive carbon black, was used. Table I displays the properties of this carbon black. 14 The highly branched, high surface area carbon black structure allows it to contact a large amount of

TABLE I

structure allows it to contact a large amount of TABLE I Properties of Akzo Nobel Kejenblack
structure allows it to contact a large amount of TABLE I Properties of Akzo Nobel Kejenblack

Properties of Akzo Nobel Kejenblack EC-600 JD Carbon Black 14

Electrical resistivity of

Size of carbon black

0.010.1 cm

carbon black Product form

aggregates Specic gravity

Pellet in size from 100 µm to a few mm 30100 nm

1.8 g/cc

Bulk density

100120 kg/m 3

Ash, max

0.1 wt %

Moisture, max

0.5 wt %

BET (N 2 ) surface area

1250 m 2 /g

Pore volume (DBP-absorption)

480510 cm 3 /100 g

polymer, which results in improved electrical con- ductivity at low carbon black concentrations. Table II shows the properties of Thermocarb TM TC-300 Spe- cialty Graphite, a high quality synthetic graphite that is available from Conoco, Inc. Thermocarb was used because of its high-thermal conductivity and mod- erately high-electrical conductivity. 15 BP/Amocos pitch-based milled (200 m long) carbon ber, Ther- malGraph DKD X, was used to improve the electrical and thermal conductivity and the tensile strength of the resin. Table III shows the properties of this carbon ber. 16 In this study, a 2 3 factorial design (three factors or llers in this case at two different loading lev- els) was completed in each polymer. In addition, a complete replicate of the factorial design was also completed in each polymer. For all llers, the low- loading level was zero wt %. The high-loading level varied for each ller. The high levels were 5 wt % for Ketjenblack EC-600 JD, 30 wt % for Thermocarb TM TC-300 Specialty Graphite, and 20 wt % for Thermal- Graph DKD X. Table IV shows the factorial design formulations. Since this project focuses on producing highly conductive composites, the high-loading lev- els were chosen so that the ller amounts would be above the electrical conductivity percolation thresh- old. Another consideration was that the total wt % ller for the composite with all llers at the high

TABLE II

for the composite with all fi llers at the high TABLE II Properties of Thermocarb T
for the composite with all fi llers at the high TABLE II Properties of Thermocarb T

Properties

of

Thermocarb TM

TC-300

Specialty

Graphite 15

Ash Sulfur Vibrated bulk density Density

Electrical resistivity

<0.1 wt % 0.02 wt % 0.66 g/cc 2.24 g/cc

Particle sizing, a vol % (by Sieve Method) +48 Tyler Mesh

4

48/+80 Tyler Mesh

22

80/+200 Tyler Mesh

48

200/+325 Tyler Mesh

16

325 Tyler Mesh

10

Thermal conductivity at 23C

600 W/mK on a 6 mm particle 10 5 cm

2.0

Mean particle aspect ratio

(approximate)

Particle shape

Irregular

a 48 Tyler Mesh = 297 µm; 80 Tyler Mesh = 177 µm; 200 Tyler Mesh = 74 µm; 325 Tyler Mesh = 44 µm.

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

TABLE III

IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS TABLE III Properties of BP/Amoco ThermalGraph DKD X 1 6
IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS TABLE III Properties of BP/Amoco ThermalGraph DKD X 1 6

Properties of BP/Amoco ThermalGraph DKD X 16

Tensile strength Tensile modulus Electrical resistivity Thermal conductivity

>1.39 GPa 687927 GPa <3 µ m 400700 W/mK

Fiber density

2.152.25 g/cm 3

Bulk density Fiber diameter Filament shape Average lament length Filament length distribution

0.250.55 g/cm 3 10 µm Round 200 µm <20% less than 100 µm

Carbon assay

<20% greater than 300 µm 99+ wt %

Surface area

0.4 m 2 /g

level be 55 wt %. Higher ller amounts would likely make it difcult to extrude and injection mold the conductive resin into test specimens. Shielding effectiveness was also measured on composites containing only one type of carbon ller in both nylon 6,6 and polycarbonate. The loading levels for these single-ller composites are shown in Table V.

TEST SPECIMEN FABRICATION

For this study, the llers were used as received. Zytel 101 NC010 and Lexan HF 1110-111N were dried in an indirect heated dehumidifying drying oven (dewpoint of the recirculating air = −40 C). After drying, the polymers were stored in moisture-barrier bags.

The extruder used was an American Leistritz Ex-

truder Corporation Model ZSE 27. This extruder has

a 27 mm corotating intermeshing twin screw with

10 zones and a length/diameter ratio of 40. The screw design, displayed in Fig. 1, was chosen to ob- tain the maximum possible conductivity. Hence, a minimum amount of ller degradation was desired, while still dispersing the llers well in the polymers. The same screw design was used for the entire study. The polymer pellets (Zytel or Lexan) were intro- duced in Zone 1. The rst side stuffer, utilized to introduce carbon black and Thermocarb TM TC-300

Specialty Graphite into the polymer melt, was lo- cated at Zone 5. The second side stuffer was located

at Zone 7 and was used to introduce the carbon ber

into the polymer melt. Four Schenck AccuRate gravi- metric feeders were used to accurately control the amount of each material added to the extruder. After passing through the extruder, the polymer strands (3 mm in diameter) entered a water bath and then a pelletizer that produced nominally 3-mm long pellets. After compounding, the pelletized compos- ite resin was dried again and then stored in moisture barrier bags prior to injection molding. A Niigata injection molding machine, model

NE85UA 4 , was used to produce test specimens. This machine has a 40-mm diameter single screw with

a length/diameter ratio of 18. The lengths of the

feed, compression, and metering sections of the sin- gle screw are 396, 180, and 144 mm, respectively. A single cavity mold was used to produce 3.2-mm thick and 13.1-cm diameter disks (end gated). The SE of all formulations, except the formulation containing all three llers in polycarbonate, were determined. This highest ller loading polycarbonate-based resin was too viscous to mold.

TABLE IV

polycarbonate-based resin was too viscous to mold. TABLE IV Filler Loadings in Factorial Design Formulations for
polycarbonate-based resin was too viscous to mold. TABLE IV Filler Loadings in Factorial Design Formulations for

Filler Loadings in Factorial Design Formulations for Nylon 6,6 and Polycarbonate

Formulations

Ketjenblack EC-600 JD (wt %)

Thermocarb TM TC-300 Specialty Graphite (wt %)

ThermalGraph DKD X (wt %)

No ller

0

0

0

CB

5

0

0

SG

0

30

0

CBSG

5

30

0

CF

0

0

20

CBCF

5

0

20

SGCF

0

30

20

CBSGCF

5

30

20

CB: Carbon black; SG: Synthetic graphite (Thermocarb TM TC-300 Speciality Graphite); CF: Carbon ber.

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

TABLE V

IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS TABLE V Single Polycarbonate Filler Loading Levels for Nylon 6,6
IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS TABLE V Single Polycarbonate Filler Loading Levels for Nylon 6,6

Single

Polycarbonate

Filler

Loading

Levels

for

Nylon

6,6

and

Filler

Loading Levels (wt %)

Kejenblack EC-600 JD 2.5, 4.0 , 5.0, 6.0, 7.5, 10.0

Thermocarb TM TC-300 Specialty Graphite ThermalGraph DKD X

10.0, 15.0, 20.0, 30.0, 40.0

5.0, 10.0, 15.0, 20.0, 30.0, 40.0

SE TEST METHOD

The electromagnetic SE of each formulation was measured according to ASTM D 4935-89 (Reap- proved 1994), for planar materials using a plane- wave, far-eld EM wave. 5 This method is valid over a frequency range of 30 MHz to 1.5 GHz. An Electro- Metrics, Inc. SE test xture (model EM-2107A) was used to hold the sample. A HP 8752C network ana- lyzer was used as the signal generator and receiver. For each formulation, one reference sample and three load samples were tested at the following frequen- cies: 30, 100, 200, 300, 400, 500, 600, 700, 800, and 1000 MHz. The SE for a material is the difference

between the SE value of the load samples minus the SE value of the reference sample. The input power used was 0 dB and the tests were all conducted inside a Faraday cage to minimize interference for other electronic devices in the area. The dynamic range (difference between the maximum and min- imum signals measurable by the system) of the sys- tem was 80 dB. The nylon 6,6-based samples were all tested dry as molded (DAM). The polycarbonate- based samples were conditioned at 50% relative hu- midity for 24 h at 23 C prior to testing.

FILLER LENGTH AND ASPECT RATIO TEST METHOD

In order to determine the length of the carbon ber and synthetic graphite in the SE test specimens, sol- vent digestion was used. A 0.2 g sample cut from the SE test specimen was dissolved at 23 C using formic acid to remove the nylon 6,6 and methylene chloride to remove the polycarbonate. The llers were then dispersed onto a glass slide and viewed using an Olympus SZH10 optical microscope with an Optronics Engineering LX-750 video camera. The images (at 60× magnication) were collected using

Atmospheric Atmospheric Vent Side Stuffer Side Stuffer Back Vent Main Feed 40D 36D 32D 28D
Atmospheric
Atmospheric
Vent
Side Stuffer
Side Stuffer
Back Vent
Main Feed
40D
36D
32D
28D
24D
20D
16D
12D
8D
4D
0D
For Screw Type Elements Kneading disks GFA-d-ee-ff KS1-d-hh-i G = co-rotating KS1 = Kneading disc
For Screw Type Elements
Kneading disks
GFA-d-ee-ff
KS1-d-hh-i
G
= co-rotating
KS1 = Kneading disc
F
= conveying
d
= number of threads
A
= Free-Meshing
h
= length of kneading disc in millimeters
GFA 2-30-30
GFA 2-30-90
GFA 2-40-90
KB 5-2-30-60
KB 5-2-30-30
GFA 2-30-60
GFA 2-40-90
KB 5-2-30-90
KB 5-2-30-60
KB 5-2-30-30
GFA 2-30-60
GFA 2-40-90
GFA 2-40-90
KS 1-2-10 E
KS 1-2-10 A
KB 5-2-30-90
KB 5-2-30-60
KB 5-2-30-60
KB 5-2-30-30
GFA 2-20-30
GFA 2-30-90
GFA 2-40-90

d = number of threads

ee = pitch (length in millimeters for one complete rotation)

ff = length of screw elements in millimeters

Kneading disks

KBj-d-kk-ll

KB = kneading block

j

= number of kneading segments

d

= number of threads

k

= length of kneading block in millimeters

l

= twisting angle of the individual kneading segments

i = A for initial disc and E for end disc

Zones 0D to 4D is Zone 1 (water cooled, not heated) 4D to 8D is Zone 2 and Heating Zone 1 8D to 12D is Zone 3 and Heating Zone 2 12D to 16D is Zone 4 and Heating Zone 3 16D to 20D is Zone 5 and Heating Zone 4 20D to 24D is Zone 6 and Heating Zone 5 24D to 28D is Zone 7 and Heating Zone 6 28D to 32D is Zone 8 and Heating Zone 7 32D to 36D is Zone 9 and Heating Zone 8 36D to 40D is Zone 10 and Heating Zone 9

Nozzle is Heating Zone 10

FIGURE 1. Extruder screw design.

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

Scion Image version 1.62 software. The images were then processed using Adobe Photoshop 5.0 and the Image Processing Tool Kit version 3.0. The length and aspect ratio (length/diameter) of each ller was measured. For each formulation, between 1000 and 6000 particles/bers were measured. Because

of the extremely small size of the carbon black, the

length and aspect ratio of the carbon black was not measured.

FILLER ORIENTATION TEST METHOD

In order to determine the orientation of the car- bon llers, a polished composite sample was viewed using an optical microscope. Again, because of the

small size of the carbon black (aggregates 30100 nm

in size), the orientation of only the synthetic graphite

particles and carbon bers were determined. For each formulation, one 13 mm by 13 mm square was cut from a SE sample. This sample was mounted in epoxy such that the through the sample thickness (3.2 mm) face could be viewed. The samples were then polished and viewed using an Olympus BX60 transmitted light microscope at a magnication of 200×. Again, the images were collected using Scion Image version 1.62 software. The images were then processed using Adobe Photoshop 5.0 and the Image Processing Tool Kit version 3.0. For each formulation, the orientation was determined by viewing typically 10006000 particles/bers.

SURFACE ENERGY TEST METHOD

Surface energies for the three llers were mea- sured using the Washburn adsorption method. 17 The two components of the total surface energy, a po- lar and a dispersive component, were determined. 18 This analysis was performed using a Kruss Processor Tensiometer K12 with an FL12 powder cell accessory, and was carried out by Kruss Laboratory Services in Charlotte, NC. The total, polar, and dispersive com- ponents of the polymer surface energy were deter- mined in the melt phase (to simulate extrusion and injection molding; 270 C for nylon 6,6 and 288 C for polycarbonate) using the pendant drop tech- nique by Kruss Laboratory Services (see footnote).

A Kruss Drop Shape Analysis System DSA10 was

used.

Personal communication with Kruss Laboratory Services, Kruss USA, Charlotte, NC, August 2001.

X-RAY PHOTOELECTRIC SPECTROSCOPY

X-ray Photoelectric Spectroscopy (XPS) was used

to determine the surface composition of the various

carbon llers. Since each element has a unique set

of binding energies, XPS can determine the elements

˚

present in the top 50100 A of the sample surface.

A Perkin-Elmer PHI 1600 XPS system was used in

an ultra-high vacuum chamber. The Thermocarb TM TC-300 Specialty Graphite and the Ketjenblack EC-600 JD samples were pressed into 13-mm diam- eter wafers, using a hydraulic press. The Thermal- Graph DKD X pitch-based carbon ber was mounted on the sample holder using double-sided copper tape. 19

Results

FILLER LENGTH AND ASPECT RATIO RESULTS

Table VI shows the mean length and aspect ratio (length/diameter) results of the synthetic graphite particles and carbon bers for the factorial design formulations in both polymers after the llers were removed via solvent digestion. The values listed un- der the as receivedformulation are the length and aspect ratio of the ller prior to extrusion and injec- tion molding. 19,20 The results in Table VI show that there is a sig- nicant degradation of the carbon bers follow- ing the extrusion and injection molding steps. The mean length and aspect ratio of the as received car- bon bers was 167.5 m and 16.75, respectively. This compares well to the reported vendor litera- ture value which states a 200 m mean carbon ber length. 16 In the 20 wt % carbon ber formulation in nylon 6,6, the bers now have a mean length of 95 m (aspect ratio = 9.5). In the nylon-based composites containing both carbon bers and synthetic graphite, the mean length of the bers was 77 m (aspect ra- tio = 7.7). The ber results for the polycarbonate- based composites were similar to those of the ny- lon composites, with the length decreasing to 82 m (aspect ratio = 8.2) in the 20 wt % formulation, and then to a 71 m length (aspect ratio = 7.1) in the composite containing bers and synthetic graphite. Overall, processing reduced the carbon ber length and aspect ratio to approximately half of its as re- ceived values. These length results are comparable

to those reported by Bigg who showed that carbon

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

TABLE VI

Mean Length and Aspect Ratio Results for Factorial Design Formulations 19,20

Results for Factorial Design Formulations 1 9 , 2 0 Formulation Nylon 6,6 Length ( µ
Results for Factorial Design Formulations 1 9 , 2 0 Formulation Nylon 6,6 Length ( µ

Formulation

Nylon 6,6

Length (µm)

Aspect Ratio

Polycarbonate

Length (µm)

Aspect Ratio

As received carbon bers (CF)

167.5

16.75

167.5

16.75

As received synthetic graphite (SG)

68.3

1.80

68.3

1.80

SG only composites

74.8

1.68

43.8

1.66

SG only replicate composites

56.0

1.61

49.7

1.70

CF only composites

95.7

9.57

85.7

8.57

CF only replicate composites

94.1

9.41

81.7

8.17

CF (SGCF composites)

71.7

7.17

71.4

7.14

SG (SGCF composites)

59.7

1.84

33.6

1.67

CF (SGCF replicate composites)

82.3

8.23

70.8

7.08

SG (SGCF replicate composites)

41.9

1.72

33.0

1.67

CB: Carbon black; SG: Synthetic graphite; CF: Carbon ber.

ber/nylon 6,6 composites had ber lengths of ap- proximately 130 m after extrusion and injection molding. 21 Table VI also shows the lengths and aspect ratios of the synthetic graphite particles (Thermocarb TM TC-300 Specialty Graphite). Table VI shows that the length and aspect ratio of the synthetic graphite par- ticles in the composite specimens remain similar to that of the as received material. This result is likely due to the relatively small length and aspect ratio of the as received Thermocarb TM TC-300 Specialty Graphite. The as received synthetic graphite has a mean length of 68 m and a mean aspect ratio of 1.8. In the 30 wt % synthetic graphite formulation in nylon 6,6, the graphite particles now have a mean length of 65 m (aspect ratio = 1.65). In the nylon- based composites containing both carbon bers and synthetic graphite, the mean length of the synthetic graphite was 51 m (aspect ratio = 1.78). The results for the polycarbonate-based composites were simi- lar to those of the nylon composites.

FILLER ORIENTATION RESULTS

As discussed previously, the ller orientation an- gle was measured by optical microscopy. The an- gle of interest in these measurements was the devi- ation of the ller away from the angle of SE mea- surement. For these measurements, all of the angles will be between 0 and 90 . An angle of 0 signies that the particles/bers are aligned parallel to the SE measurement direction. An angle of 90 means that

the ller is perpendicular to the SE measurement direction. Table VII displays the orientation results (mean, standard deviation, and number of ller parti- cles/bers measured) for the composites containing only synthetic graphite (Thermocarb TM TC-300 Spe- cialty Graphite) and carbon ber. The mean orien- tation ranges from approximately 60 to 70 . Hence, the orientation angle is closer to 90 , indicating that the bers/particles are primarily orientated trans- verse to the SE measurement direction. A photo- micrograph showing this ller orientation for a composite containing 20 wt % Thermocarb TM TC- 300 Specialty Graphite in polycarbonate is located elsewhere. 22

SURFACE ENERGY AND XPS RESULTS

Table VIII displays the polar and dispersive sur- face energy components for all the materials used. The total surface energy for the pure nylon 6,6 was measured to be 45.92 mJ/m 2 in the melt phase. The pure polycarbonate has a total surface energy of 38.05 mJ/m 2 in the melt phase. The total sur- face energy of the carbon black was measured to be 21.77 mJ/m 2 . The carbon ber has a total surface energy of 22.23 mJ/m 2 , and the synthetic graphite has a total surface energy value of 24.00 mJ/m 2 . Since all the ller surfaces are composed of essen- tially pure carbon which has not been surface treated, one would expect the surface energy results for these llers to be similar.

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

TABLE VII

Single Filler Orientation Results in Nylon 6,6 and Polycarbonate 19,20

Results in Nylon 6,6 and Polycarbonate 1 9 , 2 0 Orientation ( ◦ ) Formulation
Results in Nylon 6,6 and Polycarbonate 1 9 , 2 0 Orientation ( ◦ ) Formulation

Orientation ( )

Formulation

Nylon 6,6

Polycarbonate

Synthetic graphite (wt %)

10

58.72 ± 23.92 (n = 733)

66.47 ± 21.48 (n = 2690)

15

60.24 ± 23.48 (n = 2118)

67.92 ± 20.79 (n = 3173)

20

61.55 ± 24.63 (n = 3755)

66.35 ± 22.34 (n = 5271)

30

57.46 ± 25.02 (n = 3784)

67.20 ± 22.70 (n = 4945)

40

58.25 ± 25.72 (n = 3235)

66.99 ± 22.12 (n = 1180)

Carbon ber (wt %)

5

72.48 ± 21.30 (n = 831)

77.35 ± 17.92 (n = 1636)

10

71.61 ± 21.83 (n = 2058)

69.47 ± 22.14 (n = 1819)

15

66.45 ± 24.74 (n = 2595)

66.54 ± 23.72 (n = 6321)

20

68.56 ± 22.45 (n = 4183)

64.47 ± 24.39 (n = 4599)

30

63.37 ± 23.81 (n = 4405)

61.11 ± 25.02 (n = 4014)

40

65.11 ± 22.54 (n = 4142)

62.26 ± 24.66 (n = 4516)

The surface polarity values (polar surface energy component/total surface energy) are also given in Table VIII. These results can be used to determine which polymer would provide for more complete dispersion with each of the llers. Materials that have similar surface polarity values provide im- proved dispersion in the composites. 23 The results in Table VIII indicate that the polycarbonate matrix has a surface polarity more comparable to that of the carbon llers; and hence, should provide for a more complete dispersion of each of the carbon llers ver- sus nylon 6,6. Results from the XPS analysis for all three llers used are also in Table VIII. Only two elements were present on the ller surface, carbon and oxygen. This table shows that, as expected, all the llers consisted mainly of carbon. Also, as expected, as the amount

of oxygen present on the ller surface increased, the polar component of the surface energy increased.

SE RESULTS

The SE for the composites containing only varying amounts of carbon black in both polymers is shown in Fig. 2 at 300 and 800 MHz. Each data point shown in Fig. 2 is the mean of three load samples and one reference sample tested per formulation. Figure 2 shows that adding carbon black to both resins causes the SE to increase signicantly from 0 dB for the neat polymer to approximately 22 dB for 10 wt % (6.6 vol % in nylon, 6.9 vol % in polycarbonate) car- bon black in both polymers. The SE results are similar for both polymers and for both frequencies (300 and 800 MHz).

TABLE VIII

and for both frequencies (300 and 800 MHz). TABLE VIII Surface Energy and XPS Results a
and for both frequencies (300 and 800 MHz). TABLE VIII Surface Energy and XPS Results a

Surface Energy and XPS Results a

Material

Polar Component (mJ/m 2 )

Dispersive Component (mJ/m 2 )

Total Surface Energy (mJ/m 2 )

Surface

Polarity (%)

Oxygen on Filler Surface (Atomic %)

Zytel 101 NC010

17.24

28.68

45.92

37.5

Lexan HF1110-111N

8.55

29.50

38.05

22.5

Carbon black

2.18

19.59

21.77

10.0

1.3

Synthetic graphite

3.99

20.01

24.00

16.6

1.8

Pitch-based carbon ber

5.47

16.76

22.23

24.6

3.7

a Ref. 19 and Personal Communication with Kruss Laboratory Services (Kruss USA, Charlotte, NC, August 2001).

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

25 20 15 10 5 0 Shielding Effectiveness (dB)
25
20
15
10
5
0
Shielding Effectiveness (dB)

012345678

Volume % Carbon Black

300MHz in Nylon 6,6 800 MHz in Nylon 6,6

MHz in Nylon 6,6

800 MHz in Nylon 6,6300 MHz in Nylon 6,6

300MHz in Polycarbonate 800 MHz in Polycarbonate

MHz in Polycarbonate

800 MHz in Polycarbonate300 MHz in Polycarbonate

FIGURE 2. Shielding effectiveness of composites containing only carbon black.

Figure 3 shows the SE of the 5 wt % carbon black (3.2 vol % in nylon, 3.4 vol % in polycarbonate) in both polymers over the entire frequency range mea- sured. These composites were extruded and injection molded into test specimens twice; hence, one set is labeled replicatefor each polymer in Fig. 3. From Fig. 3, one notices that the SE is approximately 2 dB higher in polycarbonate as compared to nylon. The SE results for the composites containing only varying amounts of Thermocarb TM TC-300 Specialty

Graphite, which is a high purity synthetic graphite, in both polymers are shown in Fig. 4 at 300 and 800 MHz. Figure 4 shows that adding synthetic graphite to both resins causes the SE to increase, but not as much as was evident by adding car- bon black. Typically, the SE values at 800 MHz are slightly higher than what were observed for the same material at 300 MHz. Once again, the SE of the polycarbonate-based composite is higher than that of the nylon-based composite.

18.00 16.00 14.00 12.00 10.00 8.00 6.00 4.00 2.00 0.00 0 200 400 600 800
18.00
16.00
14.00
12.00
10.00
8.00
6.00
4.00
2.00
0.00
0
200
400
600
800
1000
1200
Shielding Effectiveness
(dB)

Frequency (MHz)

Wt% Carbon Black in NylonWt% Carbon Black Replicate in Nylon Wt% Carbon Black in Polycarbonate Wt% Carbon Black Replicate

Wt% Carbon Black Replicate in NylonWt% Carbon Black in Nylon Wt% Carbon Black in Polycarbonate Wt% Carbon Black Replicate in Polycarbonate

Wt% Carbon Black in PolycarbonateWt% Carbon Black in Nylon Wt% Carbon Black Replicate in Nylon Wt% Carbon Black Replicate in

Wt% Carbon Black Replicate in PolycarbonateWt% Carbon Black in Nylon Wt% Carbon Black Replicate in Nylon Wt% Carbon Black in Polycarbonate

5

5

5

5

FIGURE 3. Shielding effectiveness of composites containing 5 wt % carbon black in nylon 6,6 and in polycarbonate.

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

14 12 10 8 6 4 2 0 0 5 10 15 20 25 30
14
12
10
8
6
4
2
0
0
5
10
15
20
25
30
Shielding Effectiveness (dB)

Volume % Thermocarb TM Specialty Graphite

300MHz in Nylon 6,6 800 MHz in Nylon 6,6

MHz in Nylon 6,6

800 MHz in Nylon 6,6300 MHz in Nylon 6,6

300MHz in Polycarbonate 800 MHz in Polycarbonate

MHz in Polycarbonate

800 MHz in Polycarbonate300 MHz in Polycarbonate

FIGURE 4. Shielding effectiveness of composites containing only Thermocarb TM TC-300 Specialty Graphite.

Figure 5 shows the SE of the 30 wt % Thermo- carb TM TC-300 Specialty Graphite (17.9 vol % in ny- lon, 18.7 vol % in polycarbonate) in both polymers over the entire frequency range measured. Once again, one notices that the SE is slightly higher in

polycarbonate as compared to nylon and that the SE increases as frequency increases. The SE results for the composites containing only varying amounts of carbon ber in both polymers are shown in Fig. 6 at 300 and 800 MHz. Figure 6 shows

7.00 6.00 5.00 4.00 3.00 2.00 1.00 0.00 0 200 400 600 800 1000 1200
7.00
6.00
5.00
4.00
3.00
2.00
1.00
0.00
0
200
400
600
800
1000
1200
Shielding Effectiveness (dB)

Frequency (MHz)

Wt% Thermocarb TM Specialty Graphite in NylonWt% Thermocarb TM Specialty Graphite Replicate in Nylon Wt% Thermocarb TM Specialty Graphite in Polycarbonate

Wt% Thermocarb TM Specialty Graphite Replicate in NylonWt% Thermocarb TM Specialty Graphite in Nylon Wt% Thermocarb TM Specialty Graphite in Polycarbonate Wt% Thermocarb

Wt% Thermocarb TM Specialty Graphite in PolycarbonateWt% Thermocarb TM Specialty Graphite Replicate in Nylon Wt% Thermocarb TM Specialty Graphite Replicate in

Wt% Thermocarb TM Specialty Graphite Replicate in PolycarbonateWt% Thermocarb TM Specialty Graphite Replicate in Nylon Wt% Thermocarb TM Specialty Graphite in Polycarbonate 30

30

30

30

30

FIGURE 5. Shielding effectiveness of composites containing 30 wt % Thermocarb TM TC-300 Specialty Graphite in nylon 6,6 and in polycarbonate.

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

20 18 16 14 12 10 8 6 4 2 0 0 5 10 15
20
18
16
14
12
10
8
6
4
2
0
0
5
10
15
20
25
30
Shielding Effectiveness (dB)

Volume % Carbon Fiber

300MHz in Nylon 6,6 800 MHz in Nylon 6,6

MHz in Nylon 6,6

800 MHz in Nylon 6,6300 MHz in Nylon 6,6

300MHz in Polycarbonate 800 MHz in Polycarbonate

MHz in Polycarbonate

800 MHz in Polycarbonate300 MHz in Polycarbonate

FIGURE 6. Shielding effectiveness of composites containing only carbon ber.

that adding carbon ber to both resins also causes

becomes more comparable to the size of the ller.

the

SE to increase. For example, at 800 MHz the SE

Thus, the higher frequency waves are more likely

was 15.5 dB for the 40 wt % carbon ber in polycar- bonate sample as compared to 12.0 dB for 40 wt %

to encounter ller embedded in the polymer matrix. The llers are more likely to reect or absorb the

Thermocarb TM TC-300 Specialty Graphite in poly- carbonate. Of all the single llers at 800 MHz, the SE was the highest at 21.9 dB for the resin containing 10 wt % carbon black in polycarbonate. The obser- vation that adding 10 wt % carbon black produced

wave, as compared to the polymer rich areas. Hence, SE increases as frequency increases. The observation of higher SE in polycarbonate as compared to nylon is interesting. Several fac- tors (ller length, orientation, and adhesion) could

a

composite with higher SE than that measured on

be involved. Longer ller lengths in polycarbonate

composites containing 40 wt % carbon ber is not surprising since the electrical resistivity (4.90 ± 0.7

could cause higher composite electrical conductiv- ity, which could cause higher SE results. However,

cm

for 10 wt % carbon black/polycarbonate; 10.5 ±

the ller length data shown in Table VI typically

1.1 cm for 40 wt % carbon ber/polycarbonate) was also lower for the composites containing carbon

indicate slightly lower ller lengths in polycarbon- ate as compared to nylon. The ller orientation re-

black. 13 Figure 7 shows the SE of the 20 wt % carbon ber

sults in Table VII indicate similar values for the polycarbonate- and nylon-based samples. The sur-

(11.7 vol % in nylon, 12.2 vol % in polycarbonate) in both polymers over the entire frequency range mea- sured. Figures 6 and 7 again show that the SE values

face energy results in Table VIII indicate that all three carbon llers have a surface polarity value closer to that of the polycarbonate (as compared to nylon).

at

800 MHz are slightly higher than what is observed

Hence, the polycarbonate, having a surface polar-

for

the same material at 300 MHz and that the SE of

ity which is more comparable to that of the carbon

the

polycarbonate-based composites are higher than

llers, should provide for more complete dispersion

that of the nylon-based composites. The observation of generally increasing SE value with increasing frequency is expected and has been noted elsewhere. 6 As frequency increases, the wave- length of the electromagnetic wave decreases and

of the ller in the conductive resin. It is speculated that this increased dispersion of the carbon llers in the polycarbonate causes the SE to be higher. Table IX shows the mean SE and standard de- viation for each factorial design formulation for

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

7.00 6.00 5.00 4.00 3.00 2.00 1.00 0.00 0 200 400 600 800 1000 1200
7.00
6.00
5.00
4.00
3.00
2.00
1.00
0.00
0
200
400
600
800
1000
1200
Shielding Effectiveness (dB)

Frequency (MHz)

Wt% Carbon Fiber in NylonWt% Carbon Fiber Replicate in Nylon Wt% Carbon Fiber in Polycarbonate Wt% Carbon Fiber Replicate

Wt% Carbon Fiber Replicate in NylonWt% Carbon Fiber in Nylon Wt% Carbon Fiber in Polycarbonate Wt% Carbon Fiber Replicate in Polycarbonate

Wt% Carbon Fiber in PolycarbonateWt% Carbon Fiber in Nylon Wt% Carbon Fiber Replicate in Nylon Wt% Carbon Fiber Replicate in

Wt% Carbon Fiber Replicate in PolycarbonateWt% Carbon Fiber in Nylon Wt% Carbon Fiber Replicate in Nylon Wt% Carbon Fiber in Polycarbonate

20

20

20

20

FIGURE 7. Shielding effectiveness of composites containing 20 wt % carbon ber in nylon 6,6 and in polycarbonate.

the nylon-based resins. Table X gives the SE re- sults for each factorial design formulation for the polycarbonate-based resins. A complete replicate of the full factorial was completed in each resin. Hence,

TABLE IX

full factorial was completed in each resin. Hence, TABLE IX Shielding Effectiveness Results at 300 and
full factorial was completed in each resin. Hence, TABLE IX Shielding Effectiveness Results at 300 and

Shielding Effectiveness Results at 300 and 800 MHz for Factorial Design Formulations in Nylon 6,6

Shielding Effectiveness (dB)

Mean

Shielding

Effectiveness

Formulation

Original

Replicate

(dB)

300

MHz

No ller

0.03 ± 0.05 0.07 ± 0.19

0.05

CB

7.35 ± 0.23 1.30 ± 0.06 23.11 ± 0.40 2.32 ± 0.16 21.00 ± 0.45 10.08 ± 0.06

7.42 ± 0.03 1.74 ± 0.08 22.90 ± 0.26 2.34 ± 0.17 20.19 ± 0.36 12.81 ± 0.23 40.88 ± 0.40

7.39

SG

1.52

CBSG

23.01

CF

2.33

CBCF

20.60

SGCF

11.45

CBSG CF 42.63 ± 0.32

41.76

800

MHz

No ller

0.10 ± 0.04 7.17 ± 0.20 2.22 ± 0.04 23.11 ± 0.10 4.24 ± 0.28 20.88 ± 0.40 13.08 ± 0.17

0.07 ± 0.05 7.18 ± 0.01 3.04 ± 0.17 23.09 ± 0.23 4.25 ± 0.13 19.89 ± 0.15 15.34 ± 0.17 42.01 ± 0.32

0.09

CB

7.18

SG

2.63

CBSG

23.10

CF

4.25

CBCF

20.39

SGCF

14.21

CBSGCF 42.44 ± 0.83

42.23

there is a column labeled Originaland Replicate.These columns show the mean and standard devi- ation. For each formulation, three load specimens and one reference sample were tested. As stated pre- viously, Table IV denes the factorial design formu- lations in both polymers.

TABLE X

factorial design formu- lations in both polymers. TABLE X Shielding Effectiveness Results at 300 and 800
factorial design formu- lations in both polymers. TABLE X Shielding Effectiveness Results at 300 and 800

Shielding Effectiveness Results at 300 and 800 MHz for Factorial Design Formulations in Polycarbonate

Shielding Effectiveness (dB)

Mean

Shielding

Effectiveness

Formulation

Original

Replicate

(dB)

300

MHz

No ller

0.10 ± 0.00 0.07 ± 0.06

0.09

CB

10.19 ± 0.25 3.03 ± 0.21 27.87 ± 0.26 3.10 ± 0.10 27.07 ± 0.06 16.95 ± 0.15

10.43 ± 0.15 3.23 ± 0.31 28.37 ± 0.89 3.43 ± 0.06 26.77 ± 0.32 17.83 ± 0.35

10.31

SG

3.13

CBSG

28.12

CF

3.27

CBCF

26.92

SGCF

17.39

800

MHz

No ller

0.00 ± 0.00 10.73 ± 0.21 5.27 ± 0.32 27.60 ± 0.10 5.43 ± 0.12 26.10 ± 0.10 18.70 ± 0.10

0.03 ± 0.06 10.83 ± 0.25 5.60 ± 0.44 27.70 ± 0.30 5.87 ± 0.06 26.33 ± 0.06 19.40 ± 0.30

0.02

CB

10.78

SG

5.44

CBSG

27.65

CF

5.65

CBCF

26.22

SGCF

19.05

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

50.00 45.00 40.00 35.00 30.00 25.00 20.00 15.00 10.00 5.00 0.00 0 200 400 600
50.00
45.00
40.00
35.00
30.00
25.00
20.00
15.00
10.00
5.00
0.00
0
200
400
600
800
1000
1200
Shielding Effectiveness (dB)

Frequency (MHz)

NylonCarbon Fiber Synthetic Graphite + Carbon Fiber Carbon Black Carbon Black + Synthetic Graphite Carbon

Carbon FiberNylon Synthetic Graphite + Carbon Fiber Carbon Black Carbon Black + Synthetic Graphite Carbon Black +

Synthetic Graphite + Carbon FiberNylon Carbon Fiber Carbon Black Carbon Black + Synthetic Graphite Carbon Black + Synthetic Graphite +

Carbon BlackNylon Carbon Fiber Synthetic Graphite + Carbon Fiber Carbon Black + Synthetic Graphite Carbon Black +

Carbon Black + Synthetic GraphiteCarbon Fiber Synthetic Graphite + Carbon Fiber Carbon Black Carbon Black + Synthetic Graphite + Carbon

Carbon Black + Synthetic Graphite + Carbon Fiber

Synthetic GraphiteBlack Carbon Black + Synthetic Graphite Carbon Black + Synthetic Graphite + Carbon Fiber Carbon Black

Carbon Black + Carbon FiberFiber Carbon Black Carbon Black + Synthetic Graphite Carbon Black + Synthetic Graphite + Carbon Fiber

FIGURE 8. Shielding effectiveness results for the nylon 6,6-based factorial design formulations.

Figure 8 shows the mean SE for the nylon-based factorial design formulations over the entire range of frequencies measured. Figure 9 shows the mean SE for the polycarbonate-based factorial design for- mulations over the entire range of frequencies mea- sured. Several observations can be made by studying the results in Tables IX and X and in Figs. 8 and 9. First, for the same formulation, the SE at 300 and 800 MHz are similar. Second, for the same for- mulation, the original and replicate SE values are similar. Third, for each formulation with the same concentration of ller, the SE is slightly higher for the polycarbonate-based resins as compared to the nylon-based resins. Fourth, the composite contain- ing all three llers in nylon at 800 MHz had a SE of 42 dB, which is higher than the any resin con- taining only one ller (maximum SE in nylon with single ller was 10 wt % carbon black at 21 dB). While it is apparent that the combinations of llers produces higher conductivity results, the exact ef- fect of the combinations is not obvious without the application of statistical experimental design calculations.

FACTORIAL DESIGN ANALYSIS: SE

Using the results shown in Tables IX and X, an analysis of the factorial design was completed. This was performed using the Minitab version 13 Statis-

tical Software package. Calculations were also per- formed using Microsoft Excel 2000 so as to verify and understand the results obtained with the Minitab calculations. For this analysis, the effects and P val- ues for the SE results were calculated. For all sta- tistical calculations, the 95% condence level was used. Factorial designs were used in the project since they are the most efcient type of experiment to de- termine the effect of each ller and any possible inter- actions between llers. By using factorials, one can determine the effect that each factor (ller) has on the system by calculating a single value to quantify the change in SE as the weight percent of a ller is in- creased. These calculated effects can then be ranked to determine which llers and combinations of llers produced a larger change. 24 The effects and P values for the nylon 6,6-based composites are given in Table XI, showing the val- ues for all of the ller combinations. Further inves- tigation of Table XI yields some important informa- tion regarding the effects that llers have on SE at 300 and 800 MHz. First, all the effect terms are pos- itive, which indicates that the addition of any ller increases the SE of the composite. Second, the ef- fects and P values are similar for 300 and 800 MHz. Third, the effect term is the largest for carbon black, which indicates that carbon black causes the largest increase in composite SE. Fourth, the effect terms for

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

30.00 25.00 20.00 15.00 10.00 5.00 0.00 0 200 400 600 800 1000 1200 Shielding
30.00
25.00
20.00
15.00
10.00
5.00
0.00
0
200
400
600
800
1000
1200
Shielding Effectiveness (dB)

Frequency (MHz)

PolycarbonateCarbon Fiber Synthetic Graphite + Carbon Fiber Carbon Black Carbon Black + Synthetic Graphite Synthetic

Carbon FiberPolycarbonate Synthetic Graphite + Carbon Fiber Carbon Black Carbon Black + Synthetic Graphite Synthetic Graphite Carbon

Synthetic Graphite + Carbon FiberPolycarbonate Carbon Fiber Carbon Black Carbon Black + Synthetic Graphite Synthetic Graphite Carbon Black + Carbon

Polycarbonate Carbon Fiber Synthetic Graphite + Carbon Fiber Carbon Black Carbon Black + Synthetic Graphite Synthetic

Carbon Black

Carbon Black + Synthetic Graphite

Synthetic GraphiteCarbon Fiber Synthetic Graphite + Carbon Fiber Carbon Black Carbon Black + Synthetic Graphite Carbon Black

Carbon Black + Carbon FiberCarbon Fiber Synthetic Graphite + Carbon Fiber Carbon Black Carbon Black + Synthetic Graphite Synthetic Graphite

FIGURE 9. Shielding effectiveness results for the polycarbonate-based factorial design formulations.

TABLE XI

polycarbonate-based factorial design formulations. TABLE XI Factorial Design Analysis for Nylon 6,6-Based Con- ductive
polycarbonate-based factorial design formulations. TABLE XI Factorial Design Analysis for Nylon 6,6-Based Con- ductive

Factorial Design Analysis for Nylon 6,6-Based Con- ductive Resins at 300 and 800 MHz

 

Term

Effect

P

300

MHz

CB SG CF CB SG CB CF SG CF

19.37

0.000

11.87

0.000

11.07

0.000

6.52

0.000

4.91

0.000

3.27

0.000

CB SG CF

0.50

0.269

800

MHz

CB SG CF CB SG CB CF SG CF CB SG CF

17.93

0.000

12.57

0.000

12.02

0.000

6.31

0.000

4.15

0.000

3.33

0.000

0.38

0.286

synthetic graphite and carbon ber are similar, and they cause the second largest effect on SE. After synthetic graphite/carbon ber, the effect of the llers follows the following order: the combination of carbon black and synthetic graphite, the combi- nation of carbon black and carbon ber, and last the combination of synthetic graphite and carbon ber. All the single llers and two ller interactions are statistically signicant at the 95% condence level (P < 0.05). The three ller interaction (carbon black/synthetic graphite/carbon ber) is not statis- tically signicant (P > 0.05). The statistically signicant results for all the two ller interactions show that there is an effect on SE when different llers are combined. In this case, a statistically signicant interaction term indicates that the composite SE is higher than what would be expected from the additive effect of each single ller. 24 For example, the most signicant interaction was that of synthetic graphite/carbon black. This means that, for example, when synthetic graphite and carbon black were combined and added to ny- lon, then the SE of the composite increased more

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

than what would be expected from the individ- ual additive effect of synthetic graphite and carbon black. Table XII shows the results of the factorial design analysis for the polycarbonate-based composites at 300 and 800 MHz. Once again, the effects and P val- ues are similar for 300 and 800 MHz. In addition, as was the case for nylon, carbon black causes the largest increase in composite SE, followed by syn- thetic graphite and carbon ber, which once again have similar effect values. The rest of the statistically signicant effects, in order of their ability to increase SE of the composite, are the combination of carbon black and synthetic graphite, the combination of car- bon black and carbon ber, and last the combination of synthetic graphite and carbon ber. All of these llers and combinations of llers are statistically sig- nicant at the 95% condence level (P < 0.05). These results agree with what was obtained for the nylon- based composites. One important result from this study is that the combinations of two different carbon llers, namely, carbon black and synthetic graphite, carbon black and carbon ber, and synthetic graphite and carbon ber were statistically signicant. The fact that all the two ller interaction terms were signicant in- dicates that the composite SE is higher than what would be expected from the additive effect of each single ller. 24 To the authorsknowledge, this is the rst time in the literature that a synergistic effect of

TABLE XII

in the literature that a synergistic effect of TABLE XII Factorial Design Analysis for Polycarbonate-Based Conductive
in the literature that a synergistic effect of TABLE XII Factorial Design Analysis for Polycarbonate-Based Conductive

Factorial Design Analysis for Polycarbonate-Based Conductive Resins at 300 and 800 MHz

Term

Effect

P

300

MHz

CB

24.32

0.000

SG

15.97

0.000

CF

15.44

0.000

CB*SG

7.30

0.000

CB*CF

6.63

0.000

SG*CF

5.46

0.000

800

MHz

CB SG CF CB SG CB CF SG CF

21.39

0.000

15.14

0.000

14.53

0.000

5.73

0.000

4.90

0.000

3.99

0.000

combining different carbon llers on the composite SE has been observed. It is likely that conductive pathways are formed that linkthe high surface area carbon black, synthetic graphite particles, and carbon bers.

Conclusions

As a result of this study, the following conclusions can be made:

Extrusion and injection molding reduced the length and aspect ratio of the carbon ber in the conductive composites to approximately half of its original length (168 m) and as- pect ratio (16.8). However, the length (typi- cally 6070 m) and aspect ratio (typically 1.71.8) of the Thermocarb TM TC-300 Specialty Graphite in the composite specimens remain similar to that of the as received material. This high purity synthetic graphite likely main- tained its size better as compared to carbon ber since the as received Thermocarb TM TC- 300 material has a smaller length and aspect ratio.

For the SE samples, the synthetic graphite parti- cles and carbon bers are mainly oriented trans- verse to the direction of SE measurement.

By studying the SE factorial experiment results in both nylon and polycarbonate, several conclusions can be made at the 95% con- dence level for both polymers. First, car- bon black caused the largest increase in SE, followed by Thermocarb TM TC-300 Specialty Graphite and carbon ber, which have a similar effect. Adding two different llers also causes SE to increase in the following order:

Carbon Black/Thermocarb TM TC-300 Specialty Graphite> Carbon Black/Carbon Fiber> Thermo- carb TM TC-300 Specialty Graphite /Carbon Fiber

To the authorsknowledge, this is the rst time in the literature that a synergistic effect of combining different carbon llers on composite SE has been observed. It is likely that conduc- tive pathways are formed that linkthe high surface area carbon black, synthetic graphite particles, and carbon bers, which results in improved composite SE.

SHIELDING EFFECTIVENESS IN NYLON 6,6- AND POLYCARBONATE-BASED RESINS

Acknowledgments

The authors thank Conoco, Akzo Nobel, BP/Amoco, and DuPont for providing polymers and carbon llers.

References

1. Donnet, J.-B.; Bansal, R. C.; Wang, M.-J. Carbon Black, 2nd ed.; Marcel Dekker: New York, 1993.

2. Huang, J.-C. Adv Polym Technol 2002, 21, 299.

3. Bigg, D. M. Polym Compos 1987, 8, 1.

4. White, D. R. J. A Handbook Series on Electromagnetic Interference and Compatibility; Don White Consulatants, Germantown, MD, 1971; Vol. 5.

5. ASTM Standard D 4935-89 Reapproved 1994; American Society for Testing and Materials, Philadelphia, PA, 1996.

6. Bushko, W. C.; Stokes, V. K.; Wilson, J. In Proceedings of the Society of Plastics Engineers Annual Technical Conference, ANTEC 1999, New York, May 1999; p. 1499.

7. Bigg, D. M. Adv Polym Technol 1984, 4, 255.

8. Bigg, D. M. Polym Engr Sci 1977, 17, 842.

9. Versieck, J. In Proceedings of the Society of Plastics Engi- neers Annual Technical Conference, ANTEC 2000, Orlando, FL, May 2000; p. 1438.

10. Murthy, M. In Society of Plastics Engineers Regional Technical Conference, Chicago, IL, June 1988.

11. DuPont Zytel Nylon Resin Product and Properties, DuPont Engineering Polymers, Version 95.9; Wilmington, DE.

12. GE Engineering Thermoplastics Product Guide: Lexan PC Resin, CDC-6621 (2/98) CA; GE Plastics, Pittseld, MA 01201.

13. Clingerman, M. L.; Weber, E. H.; King, J. A. Polym Compos 2002, 23, 911.

14. Akzo Nobel Electrically Conductive Ketjenblack Product

Literature; 300 S. Riverside Plaza, Chicago, IL 60606,

1999.

15. Conoco Carbon Products Product Literature; Conoco Inc., Houston, TX 77252-2197, 1999.

16. Amoco Performance Products: High Thermal Conductivity Pitch Based Graphite Fibers; Amoco Polymers, Alpharetta, GA 30005.

17. Rulison, C. Kruss Technical Note No. 302; Kruss USA, Charlotte, NC.

18. Fowkes, F. M. Industrial and Engineering Chemistry 1964, 56,

40.

19. Clingerman, M. L. Development and Modelling of Electri- cally Conductive Composite Materials, Ph.D. Dissertation; Michigan Technological University, Houghton, MI, 2001.

20. Weber, E. H. Development and Modeling of Thermally Con- ductive Polymer/Carbon Composites, Ph.D. Dissertation; Michigan Technological University, Houghton, MI,

2001.

21. Bigg, D. M. Polym Compos 1985, 6, 20.

22. Weber, E. H.; Clingerman, M. L.; King, J. A. J Appl Polym Sci 2003, 88(1), 112.

23. Rulison, C. In 24th Annual Meeting of Adhesion Society, Williamsburg, VA, March 2001.

24. Montgomery, D. C. Design and Analysis of Experiments, 5th ed.; Wiley: New York, 2001.