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Silanes and Their Use with Boron Nitride Powders
SpecialChem | Donal McNally - Jan 8, 2014

One Row Down
In the Periodic Table, directly beneath carbon lies an element we seldom think about, even though
it is all around us. That element is silicon. Its compounds account for more than 90% of the Earth's
crust and it is estimated to be the eighth most common el ement in the universe by mass. Going
down the column of materials beneath carbon, after silicon comes the metalloid germanium,
followed by tin and lead, which are clearly metals. However, carbon is clearly not a metal, so where
does silicon belong? It has a "neither fish nor flesh" attribute and that makes it very interesting.
As we sit on the beach, or look out our windows, we are confronted with silica, the dioxide of
silicon, a solid material utterly unlike the much-maligned gaseous dioxide of carbon, the element
immediately above it in the Periodic Table. We tend to think of silicon as more like metals than like
carbon, especially when we see it used in photocell applications. Controversy about silicon's
character dates back to its discovery. In 1808, it was given the name silicium, with the -ium word-
ending suggesting to be a metal. However, its final English name, first suggested in 1817, reflects
the more physically similar elements carbon and boron. It was first prepared and characterized in
pure form in 1823.
Though less reactive than its chemical analog carbon, silicon shares with it the
ability to form chemical bonds with four hydrogen atoms arranged at the
corners of a tetrahedron. The simple compound SiH4 is analogous to methane,
CH4 and so is called monosilane. Although monosilane and disilane were already
known at the time, it was not until less than 100 years ago that Alfred Stock and
Carl Somiesky prepared the next four members of the homologous series,
SnH2n+2. Silane chemistry has expanded greatly since then.
Silanes are very reactive and have many industrial and medical applications. Perhaps the most
common use for functionalized silanes is as coupling agents for glass and carbon fibers and other
reinforcements or fillers in various polymer matrices. Silanes have also been used to couple bio-
inert layers on titanium implants, formulate water repellents, provide masonry protection, control
graffiti and so on, such that major suppliers list more than two dozen different application areas for
these materials The key to this broad range of applications for silanes is their ability to be modified
with functional groups or to be converted to other silicon compounds. Among the more common
functionalized silanes are amino-, epoxy-, methacryl-, chloro- and alkoxy-silanes.





SiH4



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For the last half a century or so, silane compounds have been used to improve mechanical,
electrical, thermal and environmental resistance properties of polymer composite materials. In
these uses, silanes function as interface modifiers, thereby promoting adhesion, coupling, or
crosslinking. Interface improvement can be achieved by compatibilization or actual bonding.
Compatibilization is achieved by the selection of appropriate functional groups to match the filler or
reinforcement, so that wet-out of the inorganic material is enhanced. Improved wet-out enables
better stress transfer into fibrous reinforcements and reduces the critical length needed to increase
tensile and flexural strength as well as impact resistance. Reduction of microvoiding around the
filler also makes for better electrical and thermal properties. Improved wet-out also contributes to
better dispersion and less clumping of powdery fillers in polymers.
A further advantage of improved polymer/filler contact is that it reduces migration of water to the
interface. Such migration can destroy adhesion and significantly reduce exposure lifetime of
composite materials. A true coupling agent provides a water-resistant bond between the inorganic
and organic materials. The chemical and physical properties of silane coupling agents not only
enhance bond strength, but also prevent de-bonding at the interface during aging and use of the
composite.

Alkoxy-silanes (typically methoxy or ethoxy) are effective in bonding to mineral surfaces because
such surfaces typically have some degree of hydroxyl functionality. The reaction with hydroxyl
groups forms a reactive silanol entity which then condenses with hydroxyl groups on mineral
components to form chemical bonds between the silane and the substrate.

Using silane additives to improve the polymer-filler interface can provide a significant gain in
thermal properties. This is important for the development of thermally conductive but electrically
insulating materials such as are used in the die-attach adhesives, encapsulations, dielectrics and
substrates employed in electronic packaging, as well as aerospace and vehicle cooling systems,
motor and battery housings, temperature sensors, heat exchangers and other systems where
thermal energy must be dissipated.

Though by no means as conductive as pure metals, polymer composites containing carbon or
graphite fibers or nanotubes, or stainless steel fibers have been shown to offer signifi cant electrical
and thermal conductivity. Unfortunately, such compounds also have greatly reduced insulation
properties. Relatively few materials exhibit thermal conductivity while remaining electrically
insulating. Among them are diamond, aluminum nitride and boron nitride. Diamond is expensive,
even in powder form and aluminum nitride is susceptible to decomposition by water to form
aluminum hydroxide and ammonia. Boron nitride (BN) is thus the foremost candidate for use as a
thermally conducting additive.

Several authors have reported on addition of silanes to BN powder to enhance thermal
conductivity of plastic resins made with this material. US patent 7524560 B2 claims a calcination-
activated boron nitride composition having its surface treated with a silane coating layer.
Thermoset resin/BN systems were the focus of published investigations, presumably because of
their greater convenience in laboratory work.



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Thermal conductivity enhancements of epoxy resin compounds of 97% and 217% have been
reported, with an optimal silane level of 2.4% by weight of the treated BN. It should be noted that
mixing and coating with relatively low viscosity uncured epoxy resins typically gives good filler wet-
out. The high increase of 217% was achieved with multimodal particle size mixing, an approach
recommended elsewhere by Momentive, the world's largest manufacturer of Boron Nitride. In one
of the studies, further increasing the level of silane to 3.2% caused a drop in thermal conductivity,
suggesting that the silane coating served as an interlayer, thereby improving the quality of the filler-
matrix interface, but that if the coating became too thick, it became less effective, or even created
something of a thermal barrier.
Somewhat different considerations arise with thermoplastic polymer matrices because of their
considerably higher viscosity in the melt state. Manufacturing highly loaded BN compounds
presents challenges, some typical of other materials and some rather different. Key issues include
achieving and consistently maintaining the correct filler loading at an acceptable production rate,
while wetting out the BN particles to the greatest possible extent.
Momentive Performance Materials Inc., headquartered in Waterford, New York is not only the
world's largest BN manufacturer, but is also a major supplier of silanes and siloxanes for a wide
range of applications including polymer compounding. While it is known that adding a silane
treatment to a boron nitride powder will improve the thermal conductivity of a compound,
different thermoplastic resins have different chemistries and may require use of silanes with
different functional groups. The synergy between Momentive's unique in-house expertise in both
silanes and boron nitride enables them to select the optimal silane for use with BN in a broad range
of thermoplastic resins.
Momentive scientists have studied polycarbonate and nylon 6 compounds containing different
amounts of BN with varying levels of different silanes in both laboratory scale experimentation and
production scale extrusion. The tables below show values of the thermal conductivity from some
of these experiments.
Base Polymer Scale BN Level, % Silane, Y/N , W/mK
%
Improvement
Nylon 6 Lab 40 N 3.48 -
Nylon 6 Lab 40 Y 3.89 12
Nylon 6 Lab 40 Y 4.31 24
Polycarbonate Lab 40 N 2.40 -
Polycarbonate Lab 40 Y 2.87 20
Polycarbonate Extrusion 36 N 2.90 -
Polycarbonate Extrusion 38 Y 3.50 21






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During the extrusion scale-up trials of polycarbonate, mechanical properties were also measured:
Base Polymer BN Level, % Silane Y/N
Notched Izod
Impact (J/m)
% Improvement
Polycarbonate 36 N 16 -
Polycarbonate 38 Y 27 69


Base Polymer BN Level, % Silane Y/N
Tensile Strength
(MPa)
% Improvement
Polycarbonate 36 N 16 -
Polycarbonate 38 Y 27 69

For information on this and other work by Momentive boron nitride experts, please contact
Momentive through SpecialChem.