Boron Nitride in Thermoplastics:

Effect of loading, particle morphology and processing conditions

Chandrashekar Raman
Momentive Performance Materials
22557 West Lunn Road, Strongsville, OH 44149
chandra.raman@momentive.com

ABSTRACT
Boron nitride (BN) is increasingly being used as a filler in thermoplastics, primarily to increase
the thermal conductivity of the resins. Filler-reinforced plastics are being considered to replace
traditionally metal parts in a number of markets, with applications such as under-hood automotive parts,
sensors and housings for motors, LEDs, and other electronic devices.
Boron nitride is a synthetic ceramic material that is isoelectronic with carbon. Like carbon, boron
nitride exists in multiple allotropic forms. The two most common forms are hexagonal boron nitride
(hBN), a soft form with a hexagonal crystal structure comparable to graphite; and cubic boron nitride
(cBN), a hard form with a crystal structure analogous to diamond. Hexagonal boron nitride can be
converted to the cubic form using a high-temperature, high-pressure process.
Hexagonal boron nitride crystals are made of planar sheets of covalently bonded boron and
nitrogen atoms that make the a-b plane of the crystal. Van der Waal’s forces hold multiple layers of such
BN planes together in the c direction. An important consequence of this crystal structure is that the
crystals have anisotropic properties, i.e. the properties in the crystal’s a-b plane are different from the
through-plane properties. For example, the in-plane thermal conductivity has been estimated to be > 300
W/mK, while the through-plane conductivity is only about 3 W/mK.
When BN powders are used as fillers in resins, the BN-resin composite materials also
demonstrate anisotropic properties, largely determined by the orientation of the platy BN crystals in the
final part. To overcome this problem of anisotropy, boron nitride powders have been developed which
are agglomerates of single crystal. In such agglomerate grades, platy BN crystals are held together to
form a larger particle to randomize their orientation. Such BN powder grades, broadly called
agglomerate grades, demonstrate more isotropic properties than do single crystal BN grades.
One of the biggest challenges of using agglomerate BN grades is to preserve the structure
through all the processing steps. BN agglomerates are relatively weak and are likely to break down into
their component platelet crystals if sheared aggressively during processing. In the case of
thermoplastics, the BN agglomerates can break down during the extrusion step and/or the molding step.
Both the screw configuration during extrusion and the flow configuration during molding determine the
extent of shear of the BN agglomerates. These processing steps should be monitored and controlled to
preserve the agglomerates’ beneficial structure.
The thermal conductivity of single crystal platelet and agglomerate boron nitrides in a
thermoplastic resin is examined in this paper to consider and explain the effect of particle morphology.
The anisotropic properties will be characterized using through-plane and in-plane thermal conductivity
measurements on BN-plastic composite parts using laser flash measurements. The effect of screw
configuration during extrusion and molding conditions on the thermal conductivity and other physical
strength properties, such as tensile strength strain at break, will also be examined and the trade-offs will
be discussed.

INTRODUCTION:
Thermoplastic materials are gaining traction in a number of applications to replace traditionally
metal parts. Their use is especially increasing in automotive applications, since plastic parts are
significantly lighter than equivalent metal parts [1,2]. While some resins may initially be more
expensive than aluminum, they can offer other potential advantages, like eliminating costly secondary
operations. Plastics can be molded to tight specifications and complex shapes, thus eliminating
machining required for metal parts [3]. However, the applications where thermoplastic materials may be
used are limited by the materials’ electrical and thermal conductivity. To overcome these limitations,
resins are often modified with suitable fillers to increase their thermal and/or electrical conductivity.
Boron nitride (BN) has been gaining interest as a filler in thermoplastics to increase thermal
conductivity of resins. BN is unique in that it is an excellent conductor of heat, but is an electrical
insulator. This occurs because heat conduction in BN is accomplished by phonons, not free electrons,
like in metals or graphite.
Boron nitride is a synthetic ceramic material that exists in multiple allotropic forms analogous to
carbon’s allotropic forms. Hexagonal BN (hBN), a soft form of BN, has a layered structure held together
by Van der Waal’s forces, a structure similar to graphite (Figure 1). Cubic BN (cBN) has a 3D-structure
similar to diamond and is a hard form of the material. cBN is only slightly softer than diamond and has a
hardness of 9.5 on the Mohs scale.

c
b
a

Figure 1: Structure of hexagonal BN

BN AlN Al2O3 SiO2 ZnO

Thermal Properties
Thermal Conductivity (W/mK) 300+ 260 30 1.4 54
Specific Heat (J/kg-K, 25o C) 794 734 798 689 523
Theoretical Density (g/cc) 2.25 3.26 3.98 2.20 5.64
Electrical Properties
Dielectric Constant 3.9 8.8 9.7 3.8 9.8
Volume Resistivity 1015 1014 1014 1014 107
Mechanical Properties
Coefficient of Thermal Expansion (ppm/K) < 1.0 4.4 6.7 0.5 0.7
Young’s Modulus (GPa) 40 400 340 72 12
Knoop Hardness (kg/mm2) 11 1200 1500 500 387

Table 1: Typical properties of various thermal fillers

 In cases where good thermal conductivity and electrical insulation properties are required, hBN
is often preferred over alumina, aluminum nitride, silica, and zinc oxide. These competitive materials
are extremely abrasive and can cause significant wear on extrusion and molding equipment, while hBN
is extremely soft, with a Mohs hardness of about 1.5. Table 1 shows the comparative typical physical
data of these fillers and also lists the Knoop Hardness, another measure of material hardness. The data
reveals that hBN is significantly softer than the competitive fillers and is, therefore, likely to have a
much lower wear impact on processing equipment.
One of the consequences of the layered structure of hBN is that it is anisotropic. Several physical
properties – such as coefficient of thermal expansion, refractive index, and thermal conductivity – are
different in the crystal plane versus through the crystal plane. The anisotropy in thermal conductivity is
especially significant; the in-plane conductivity is estimated to be as high as 300 W/mK [4], whereas the
through-plane conductivity is only about 3 W/mK [5]. The low through-plane conductivity is attributed
to poor phonon transfer in the Van der Waal’s forces that hold the parallel crystal planes together.

TEST RESULTS
Composites of high density polyethylene (HDPE) and several grades of boron nitride were
compounded at various loadings, and the thermal conductivity and mechanical strength properties of
these composites were measured.
Figure 2 shows the in-plane and through-plane conductivity of BN grade PT110-HDPE
composites. We can see that the anisotropy of the BN crystals is manifested in the final composites,
indicating that the crystal platelets are well aligned in the composite material. With increasing grade
PT110 loading, the through-plane thermal conductivity shows moderate increases, whereas the in-plane
thermal conductivity increases significantly. At 60-wt% loading, the in-plane conductivity is almost 6
W/mK. At about 15 times the conductivity of the neat resin (~ 0.4 W/mK), this represents a substantial
improvement.
7.0
Thru-plane
6.0
In-plane
Thermal Conductivity (W/mK)

5.0

4.0

3.0

2.0

1.0

0.0
30% 40% 50% 60%
BN Loading (Wt%)

Figure 2: In-plane and through-plane thermal conductivity of BN grade PT110-HDPE composites

 7.0
PT120
6.0 PT110

Thermal Conductivity (W/mK)

5.0

4.0

3.0

2.0

1.0

0.0
30% 40% 50% 60%
BN Loading (Wt%)

Figure 3: In-plane thermal conductivities of HDPE composites with BN grades PT120 and PT110.

Figure 3 shows a comparison of the thermal conductivity of HDPE compounded with two
different BN powder grades: PT120 and PT110. Both BN grades are single crystal grades, but the
average crystal size of PT110 is larger than that of PT120, as discussed in the Materials and Methods
section. We can see that grade PT110 offers higher thermal conductivities, consistent with percolation
theory. Heat conduction in such composite materials occurs through conductive paths made by contact
between filler particles in the composite. Heat transport is disrupted at the interfaces between the resin
and the filler’s particles due to phonon scattering. Hence, fewer resin-filler interfaces in the composite
ensure less phonon scattering and, therefore, greater thermal conductivity. In the present case, grade
PT110, with larger particles and fewer interfaces with HDPE than grade PT120, offers higher thermal
conductivity in the composite.
The effect of BN particle morphology on the through-plane thermal conductivity of BN-HDPE
composites was also examined in this study. Figure 4 shows the through-plane conductivity of HDPE
composites with grades PT120 and PT350. Grade PT120 is a single crystal BN grade, while grade
PT350 is an agglomerate BN grade with a crystal size comparable to grade PT120. The differences
between these grades are explained in detail in the Materials and Methods section. We can see that grade
PT350 offers higher through-plane conductivity due to its agglomerate structure. This data highlights the
significance of particle morphology on through-plane thermal conductivity. For applications where the
through-plane conductivity is a critical requirement, it is important to consider agglomerated BN powder
grades. One of the limitations of agglomerated BN grades is that they can break down to their
component platelets during compounding and molding steps because the agglomerates are relatively
weak. Figure 5 shows in-plane and through-plane thermal conductivity of grade PT350-HDPE
composites. We can see that, although grade PT350 is an agglomerate grade, the composite material
shows anisotropic thermal conductivity, indicating that a significant amount of the BN has been broken
down to single crystal platelets in the processing steps.
The intensity of mixing in a twin-screw extruder is largely determined by the screw
configuration. The screws can be designed with various mixing, conveying, and back flow elements to
control the mixing process during extrusion. The effect of screw design was examined using two
different screw configurations to compound grade PTX60, a special spherical agglomerate BN powder.
The two different screw configurations used are shown in Figure 6. Configuration 1 has one mixing
section, whereas Configuration 2 has two mixing sections.
1.8
PT120
1.6
TP Thermal Conductivity (W/mK) PT350
1.4

1.2

1.0

0.8

0.6

0.4

0.2

0.0
30% 40% 50% 60%
BN Loading (Wt%)

Figure 4: Through-plane thermal conductivity of HDPE composites with BN grades PT120 and PT350.

7.0
Thru-plane
6.0 In-plane
Thermal Conductivity (W/mK)

5.0

4.0

3.0

2.0

1.0

0.0
30% 40% 50% 60%
BN Loading (Wt%)

Figure 5: In-plane and through-plane conductivities of BN grade PT350-HDPE composites

Figure 7 shows that, at higher loadings, the through-plane conductivity of grade PTX60-HDPE
composites is higher when using Configuration 1. This data indicates that more grade PTX60 particles
are able to maintain their agglomerate structure due to less intensive mixing in Configuration 1, leading
to higher through-plane conductivity. However, it is important to highlight that the compounding
process is more difficult to control with Configuration 1. The dispersion of BN in the strands was
observed to be less uniform and powder accumulation was observed occasionally at the die exit. The die
exit pressure was also significantly higher in this case, which may be due to the powder accumulation.

Configuration 2

Configuration 1

Figure 6: Screw configurations used to compound grade PTX60 and HDPE

2.5
Config-1
Config-2
2.0
Thermal Conductivity (W/mK)

1.5

1.0

0.5

0.0
30% 40% 50% 60%
BN Loading (Wt%)

Figure 7: Impact of compounding screw configuration on through-plane conductivity of grade PTX60-HDPE composites

Similarly, the shear experienced by the BN particles during the molding step can also have a
significant impact on the structure of BN agglomerates in the composite. Figure 8 shows the through-
plane conductivity of grade PTX60-HDPE composites when molded to 1 mm thick discs and 3.2 mm
thick ASTM standard tensile bars (“dog bones”). The dog bones show a significantly higher through-
plane thermal conductivity than do the discs, indicating a greater BN particle break down in the disc
shape. This is most likely due to the higher shear rates experienced by the BN agglomerates in the disc
mold, due to the thinner mold gap.
It is also important to examine the effect of filler loading on the mechanical strength properties
of the composites. Figures 9-11 show the impact of filler loading by grade on notched Izod impact
strength, tensile strength at break, and Young’s modulus. With increasing filler content, the composites
become more brittle, as seen in the impact strength measurement. The neat resin has an impact strength
of 0.23 ft-lb/inch (from the manufacturer’s data sheet), but with just 30-wt% loading of BN powder, the
impact strength of the composite drops to less than half of that of the neat resin. The tensile strength and
Young’s modulus increase with filler loading, as expected when mineral fillers are loaded in
thermoplastic materials. The loss of physical strength presents a tradeoff to the higher thermal
conductivity that can be achieved with filler loading in these systems.

1.6

Disc
1.4
Dog bone
Thermal Conductivity (W/mK)

1.2

1.0

0.8

0.6

0.4

0.2

0.0
30% 40% 50% 60%
BN Loading (Wt%)
Figure 8: Effect of mold configuration on through-plane thermal conductivity of grade PTX60-HDPE composites

0.18

0.16 PT110
PT350
Notched Impact Strength (lb/ft-inch)

0.14 PT120
PTX60
0.12

0.10

0.08

0.06

0.04

0.02

0.00
30% 40% 50% 60%
Loading (Wt%)
Figure 9: Notched impact strength of BN-HDPE composites
 400.0

350.0 PT110
PT350
300.0 PT120
Young's Modulus (ksi)

PTX60
250.0

200.0

150.0

100.0

50.0

0.0
30% 40% 50% 60%
Loading (Wt%)
Figure 10: Young’s modulus of BN-HDPE composites

4000.0

3500.0
Tensile Strength at Break (psi)

3000.0

2500.0 PT110
PT350
2000.0
PT120
PTX60
1500.0

1000.0

500.0

0.0
30% 40% 50% 60%
Loading (Wt%)
Figure 11: Tensile strength at break of BN-HDPE composites

MATERIALS AND METHODS:

Grades of boron nitride used:

For this study, four grades of boron nitride were compounded with high density polyethylene
(HDPE). The grades used were PT120, PT110, PTX60, and PT350. The typical properties of these
various grades of BN are shown in Table 2. All are high purity BN grades, with low boric oxide and
soluble borate impurities.

PT120 PT110 PTX60 PT350

Single Crystal Single Crystal Agglomerate Agglomerate
Surface Area (m2/g) 3.5 0.5 6.0 5.0
Tap density (g/cc) 0.35 0.41 0.40 0.71
Crystal size (µµm) 10 45 8 10
Particle size, D50 (µ
µm) 10 45 60 150

Table 2: Typical properties of BN grades used

While hBN crystals are inherently platy and anisotropic, special agglomerate grades of BN
powders are available from Momentive Performance Materials that can help overcome this problem. In
these grades, a number of single crystals of BN platelets are aggregated randomly to form a larger
particle. As a result, the final particle is more isotropic than the individual component platelets. Among
the powders used in this study, grades PT120 and PT110 are single crystal powders, while grades
PTX60 and PT350 are agglomerate powders.

Processing:
Dow 17450N HDPE was extruded with various grades of boron nitride made by Momentive
Performance Materials in a 30.5 mm Werner & Pfleiderer® ZSK-30 co-rotating twin-screw extruder
(L/D ratio 28.5), through a 2 mm strand die with a die exit temperature of 190 oC at the Department of
Polymer Engineering at the University of Akron. The HDPE and BN powders were first blended before
being fed together at the feed throat via an Accurate® screw feeder. The extruder was run at 100 rpm
and the feed rate of the feeder was adjusted to ensure no accumulation in the feed throat. The extruded
strands were chopped and injection molded on a Van Dorn® 55 ton machine to make ASTM standard
tensile bars (dog bones) and 3-inch diameter, 1 mm thick discs.

Thermal conductivity testing:

Half-inch discs of HDPE-BN composite were drilled from the tab section of the dog bone tensile
bars, away from the mold gate. The discs were coated with three light coats of graphite and the through-
plane thermal conductivity was measured on a Netzsch® Nanoflash LFA447 at 25 oC, along with
appropriate Pyrex® standards to measure the specific heat. Laminates (10 mm x 10 mm) were made to
measure the in-plane thermal conductivity, also from the tab portion of the dog bone bars. The procedure
to make these laminates is shown in Figure 12. Using this procedure, the in-plane thermal conductivity
was measured using a through-plane procedure because the tensile bars are too thick for a direct in-plane
measurement, which requires 1” samples < 0.3 mm thick. The through-plane thermal conductivities
reported are the average of measurements on three discs for each sample. Only one in-plane laminate
was measured for each sample. To compare the effect of molding condition, through-plane conductivity
was also measured on half-inch discs drilled from the center of 1 mm thick discs.

Very thin layer of

epoxy adhesive
Figure 12: Procedure to make laminates for in-plane thermal conductivity measurements.
Mechanical Testing:
The tensile strength, elongation at break, and Young’s modulus were measured using an
Instron® 4465 with a pull rate of 1 inch per minute. Two and a half inch long bars were cut from the dog
bones and notched on a TMI notching cutter at a notching speed of 230 and a feed rate of 10. Notched
impact strength was measured on a TMI Impact tester using a 2 ft-lb pendulum. Complete breaks were
seen in all samples.

CONCLUSIONS:
Hexagonal boron nitride is a soft ceramic filler that is an excellent candidate to consider to
improve thermal conductivity of thermoplastic materials. The anisotropic nature of hBN crystals
translates to anisotropy in the final composites, and is therefore an important design consideration. The
in-plane thermal conductivity is affected by BN crystal size, with larger crystals showing higher thermal
conductivity. At 60-wt%, the in-plane thermal conductivity can be as high as 15 times that of the neat
resin. This study also shows that the structure of BN powders can have a significant impact on the
through-plane thermal conductivity of the composites, but that these agglomerates can break down
during the processing steps into the component single crystal platelets. The screw configuration used
during extrusion was shown to affect the extent of break down of BN agglomerates during
compounding, thus affecting the through-plane conductivity of the composites. The molding step was
also shown to affect the particle break down of BN agglomerates.

Werner & Pfleiderer® is a registered trademark of Combake International, Werner & Pfleiderer Industrial Baking
Technology.
Accurate® is a registered trademark of Schenck Accurate Inc.
Van Dorn® is a registered trademark of Van Dorn Demag Corporation.
Netzsch® is a registered trademark of Erich Netzsch GmbH & Co. Holding KG.
Pyrex® is a registered trademark of Corning Incorporated.
Instron® is a registered trademark of Illinois Tool Works Inc.

ACKNOWLEDGEMENT
The author would like to thank Rebecca Ackerman and Richard Wojciak of Momentive
Performance Materials for their help with thermal conductivity and mechanical strength measurements.

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