January 2016 

NASA/TP–2016-219001 

Radio Frequency Plasma Synthesis of Boron 

Nitride Nanotubes (BNNTs) for Structural 

Applications: Part ,

Stephen J. Hales

Langley Research Center, Hampton, Virginia 

Joel A. Alexa 

Analytical Mechanics Associates, Inc., Hampton, Virginia 

Brian J. Jensen and Donald L. Thomsen 

Langley Research Center, Hampton, Virginia 
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January 2016 

NASA/TP–2016-219001 

Radio Frequency Plasma Sysnthesis of Boron 

Nitride Nanotubes (BNNTs) for Structural 

Applications: Part ,

Stephen J. Hales 

Langley Research Center, Hampton, Virginia 

Joel A. Alexa 

Analytical Mechanics Associates, Inc., Hampton, Virginia 

Brian J. Jensen and Donald L. Thomsen

Langley Research Center, Hampton, Virginia 
Available from: 

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NASA Langley Research Center 

Hampton, VA 23681-2199 

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Space Administration. 
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

(BNNTs) for Structural Applications: Part I

ii

Abstract

It is evident that nanotubes, such as carbon, boron nitride and even silicon, offer great potential 

for many aerospace applications. The opportunity exists to harness the extremely high strength 

and stiffness exhibited by high-purity, low-defect nanotubes in structural materials. Even though 

the technology associated with carbon nanotube (CNT) development is mature, the mechanical 

property benefits have yet to be fully realized. Boron nitride nanotubes (BNNTs) offer similar 

structural benefits, but exhibit superior chemical and thermal stability. A broader range of 

potential structural applications results, particularly as reinforcing agents for metal- and ceramicbased composites. However, synthesis of BNNTs is more challenging than CNTs mainly 

because of the higher processing temperatures required, and mass production techniques have yet 

to emerge. A promising technique is radio frequency plasma spray (RFPS), which is an 

inductively coupled, very high temperature process. The lack of electrodes and the selfcontained, inert gas environment lend themselves to an ultraclean product. It is the aim of this 

White Paper to survey the state of the art with regard to nano-material production by analyzing 

the pros and cons of existing methods. The intention is to combine the best concepts and apply 

the NASA Langley Research Center (LaRC) RFPS facility to reliably synthesize large quantities 

of consistent, high-purity BNNTs.
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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Table of Contents

1. Introduction............................................................................................................................. 1

2. Candidates for Processing of BNNTs..................................................................................... 4

2.1. Incumbent Synthesis Techniques..................................................................................... 4

2.2. Direct Current (DC) Plasma Synthesis ............................................................................ 6

2.3. RF Thermal Plasma Synthesis........................................................................................ 11

2.4. RF Plasma-Chemical Synthesis ..................................................................................... 16

2.4.1. Silicon Carbide Nano-powders Produced Inside the Plasma Discharge Zone ....... 16

2.4.2. Titanium Nitride Nano-powders Produced Outside the Plasma Discharge Zone... 16

3. Proposed LaRC RFPS Approach .......................................................................................... 18

3.1. Processing Philosophy.................................................................................................... 18

3.2. Characteristics of the Facility......................................................................................... 19

3.3. Facility Modifications for BNNT Synthesis .................................................................. 20

3.4. Experimental Methodology............................................................................................ 22

3.4.1. Thermal Plasma Processing .................................................................................... 22

3.4.2. Plasma-Chemical Processing.................................................................................. 24

3.4.3. Manageable Experimental Matrix........................................................................... 24

3.5. Projected Outcome ......................................................................................................... 24

4. Concluding Remarks............................................................................................................. 26

5. References............................................................................................................................. 27

Appendix A................................................................................................................................... 31
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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Table of Figures

Figure 1. Radio frequency plasma synthesis; (a) Inductively-coupled plasma generated by 

high-frequency discharge (ref. 5); (b) NASA LaRC RF plasma spray facility...........2

Figure 2. Nanotube architecture: (a), Types of single-walled BNNTs; (i) arm-chair (10,10),

(ii) zig-zag (20,0), (iii) chiral (10,3) (ref. 6); and (b), Relative diameters of single-

[blue], double- [green], and multi-walled [red] NTs (ref. 7).......................................2

Figure 3. BOCVD method for synthesizing BNNTs (ref. 12)....................................................4

Figure 4. Concept behind most high-temperature processing methods (ref. 16)........................5

Figure 5. Pressurized vapor/condenser method; (a) Schematic of JL/NIA/LaRC PVC 

technique for synthesizing BNNTs; (b) Typical BNNT yarn produced using the 

PVC approach (ref. 17)................................................................................................6

Figure 6. DC plasma process with reaction occurring outside the discharge zone; (a) 

Transferred arc torch, using solid precursors as the target; (b) Non-transferred arc 

torch, using radial injection of solid precursors (ref. 20) ............................................7

Figure 7. DC plasma process using radial injection of liquid precursors, and reaction 

occurring inside the discharge zone (ref. 21) ..............................................................8

Figure 8. DC plasma process using radial injection of solid precursors, and reaction occurring 

inside the discharge zone (ref. 22)...............................................................................8

Figure 9. DC plasma process using radial injection of solid precursors, and reaction occurring 

outside the discharge zone (refs. 18, and 25) ............................................................10

Figure 10. Characteristics of RF torches manufactured by Tekna Plasma Systems, Inc.; (a) 

Construction schematics; (i) a torch body; (ii) the inner workings (ref. 23); (b)

Typical thermal profiles [calculated]; (i) PL-50; (ii) PL-70 (ref. 26)........................12

Figure 11. Tekna Plasma Systems, Inc.; (a) Industrial facility for spheroidization of bulk 

powder (ref. 5); (b) Induction plasma installation for nanopowders synthesis (inert 

environment) (ref. 28); (c) Schematic of equipment supporting RF torch operation 

(ref. 27); (d) Typical settings for a Tekna PL-35 torch (ref. 27)...............................13

Figure 12. University of Sherbrooke; (a) Mathematical modeling of temperature profile during 

CNT synthesis; (b) Schematic of apparatus used for RF plasma processing of 

SWCNT sheets; (c) Typical characteristics of product (ref. 29).. .............................14

Figure 13. Significant features of University of Sherbrooke apparatus; (a) Construction of 

synthesis chambers; (b) CNT collection unit geometry (ref. 29)..............................15

Figure 14. Potential replacement of sequential reaction/quenching chambers; (a) LaRC facility; 

single 1 m diameter x 1 m long chamber; (b) Tekna facility; dual 0.4 m diameter x 

0.5 m long chambers (ref. 5) .....................................................................................15

Figure 15. RF plasma process using axial injection of solid and gaseous precursors, with 

reaction occurring inside the discharge zone (refs. 24, and 32) ................................17
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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v

Figure 16. RF plasma process using radial injection of liquid and gaseous precursors, with 

reaction occurring outside the discharge zone (refs. 24, and 32). .............................17

Figure 17. Pressure vs. Temperature phase diagrams; (a) pure carbon (ref. 34); (b) pure boron 

(ref. 35); (c) boron nitride (ref. 36)............................................................................18

Figure 18. Radio frequency plasma spray facility located at NASA LaRC; (a) Features of the 

processing unit; (b) Deposition on fabric-wrapped mandrel.....................................20

Figure 19. Gas control in LaRC RFPS facility; (a) Inlet gases; (b) Outlet gases. ......................19

Figure 20. Tekna RF plasma torch; (a) Anatomy of a typical torch (refs. 23, and 30); (b) 

Adjustable height axial injection probe (ref. 19); (c) Modular installation of PL-70 

torch at LaRC. ...........................................................................................................21

Figure 21. Important features of LaRC RFPS facility; (a) Mandrel retraction to permit freeflight synthesis; (b) Chamber interior showing auxiliary access ports......................22

Figure 22. Candidate continuous collection devices for LaRC RFPS facility; (a) High volume 

cyclone separation concept (ref. 41); (b) Principle behind high volume electrostatic 

drum separators (ref. 42). ..........................................................................................23

Figure A-1. Prototype RF plasma reactor developed for synthesis of CNTs (ref. 45). ................31
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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Symbols and Abbreviations

Abbreviations

BNNT...............................boron nitride nanotube

BOCVD............................boric oxide chemical vapor deposition

CNT..................................carbon nanotube

CVD.................................chemical vapor deposition

DC....................................direct current

DWNT..............................double-walled nanotube

h-BN.................................hexagonal boron nitride

JL......................................Jefferson Lab

LaRC................................Langley Research Center

MWNT.............................multi-walled nanotube

NIA ..................................National Institute of Aerospace

NRC-C .............................National Research Council - Canada

NT ....................................nanotube

PVC..................................pressurized vapor/condenser 

RF.....................................radio frequency

RFPS ................................radio frequency plasma spray

slpm..................................standard liters per minute

SWNT ..............................single-walled nanotube
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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1

1. Introduction

There has been a great deal of aggressive promotion regarding the use of nanotubes in a wide 

variety of applications. Indeed, the projected physical and mechanical properties are very 

appealing, but taking advantage of them has proved to be problematic. Among the potential 

applications, it is evident that using nanotubes as reinforcing agents for structural materials may 

be the most challenging (ref. 1). Although carbon nanotubes (CNTs) are now mass-produced, 

the technology surrounding CNT-reinforced composites is still in its infancy. The crystal 

structure and physical morphology of boron nitride nanotubes (BNNTs) are analogous to CNTs. 

BNNTs offer the same potential benefits as CNTs, but exhibit superior chemical and thermal 

stability (ref. 2). In contrast with CNTs, which are conductors, BNNTs are insulators. These 

combined characteristics make BNNTs more compatible with metal-matrix composites, i.e. no 

fiber-matrix galvanic interactions and much higher temperature application. An additional 

benefit of BNNT-reinforced composites is that a boron-containing structural material may also

provide protection against certain types of radiation (ref. 3). However, such real-world 

applications will only emerge if commercial quantities of high-quality BNNTs are available to 

the aerospace industry.

In the case of CNTs, the production of single-walled (SWNTs), double-walled (DWNTs), or 

multi-walled (MWNTs) nanotubes represents a mature technology. In contrast, the high 

temperatures and chemical reactions associated with synthesis of BNNTs have severely 

restricted the quality and quantity of products available (ref. 2). The best nanotubes have been

formed when synthesis is conducted above the vaporization point of boron (T ~ 4000°C). 

Incumbent manufacturing techniques tend to be slow because they are batch-style processes 

which employ consumable electrodes or targets (ref. 4). The application of radio frequency 

plasma spray (RFPS) technology may be an attractive alternative for cost-effective synthesis of 

high-purity, low-defect BNNTs (ref. 5). The electrodeless, inductively-coupled process offers 

very high temperatures (T > 10,000°C) in an inert, low-pressure environment (fig. 1a). This

rapid, semi-continuous processing capability is available at the Langley Research Center 

(LaRC), and the RFPS facility represents an opportunity to investigate mass production of high 

quality BNNTs (fig. 1b). The purpose of this paper is to provide a survey of the incumbent 

BNNT synthesis techniques, and identify processing concepts and methodologies applicable to 

the proposed LaRC effort.

BNNTs are a structural analog of CNTs, replacing C atom pairs with alternating B and N atoms 

in a tubular structure (fig. 2) (ref. 6). The three principal crystal structures associated with 

SWNTs are shown in figure 2a, and the relative dimensions of SWNTs, DWNTs, and MWNTs 

are illustrated in figure 2b, colored blue, green and red, respectively (ref. 7). Processing studies 

have established that the crystal structure and morphology (number of concentric shells) are

dependent on the synthesis method employed (ref. 3). In any manifestation, BNNTs offer the 

highest potential as reinforcing agents for metal matrices, providing that the product is highpurity and defect-free. Based on specific properties, SWNTs are stronger by weight, and 

MWNTs are stronger by volume (ref. 1). This suggests that synthesis of small-diameter SWNTs 

for aerospace composite/hybrid materials, in which weight is critical, may be an appropriate

target for future development.
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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Figure 1. Radio frequency plasma synthesis; (a) Inductively-coupled plasma 

generated by high-frequency discharge (ref. 5); (b) NASA LaRC RF plasma 

spray facility.

Figure 2. Nanotube architecture: (a), Types of single-walled BNNTs; (i) arm-chair

(10,10), (ii) zig-zag (20,0), (iii) chiral (10,3) (ref. 6); and (b), Relative diameters 

of single- [blue], double- [green], and multi-walled [red] NTs (ref. 7).

Regardless of nanotube diameter, a preliminary assessment of the use of BNNTs as structural 

reinforcement of metal-matrix composites reveals some important considerations:

 Improved thermal oxidative stability of BNNT versus CNT

o In contrast with CNTs, which have a maximum use temperature of ~500°C, in the 

presence of oxygen, BNNTs are stable to ~1000°C (ref. 8). Consequently, CNTs 
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

(BNNTs) for Structural Applications: Part I

3

will likely be restricted to polymer-matrix composite applications, whereas BNNTs 

are also thermally compatible with metal- and ceramic-matrix composites. 

Fiber/matrix reactions and the use of fiber barrier coatings to mitigate such 

reactions may still be warranted in structural material applications.

 Adhesion at the fiber-matrix interface

o As with any fiber-reinforced material, the physical characteristics of the interface 

will exert a strong influence on the mechanical properties of the composite. Like 

carbon fibers, brittle carbide phases can form on CNTs during elevated temperature 

exposure (ref. 9). CNTs are electrically conductive and intimate contact with 

metals results in the creation of a galvanic couple, and accelerated corrosion ensues. 

BNNTs are chemically inert dielectric materials, so both of these issues are 

avoided.

 Fiber-matrix contact area

o Experience with discontinuous reinforcement of composites suggests that, for the 

same volume fraction, fiber dimensions are critical, i.e. length:diameter ratio (ref. 

10). A high-aspect ratio, approaching 104, is necessary for the mechanical 

properties of a discontinuous-reinforced composite to be commensurate with those 

of its continuous-reinforced counterpart. It follows that BNNTs ~10 nm in diameter 

must be ~100 μm long in order for the mechanical properties of the reinforcing 

agents to be fully conveyed to the metal matrix.

 Fiber fraction and distribution

o Dispersion of BNNTs within a metal matrix will be an important element in 

harnessing the mechanical properties (ref. 11). As with traditional reinforcing 

agents, homogeneous mixing and alignment of the fibers in the appropriate volume 

fraction will be critical. Discontinuous-reinforced composites, with randomlyoriented strands, might be a realistic, intermediate goal for the application of 

BNNTs in structures.

Historically, the production of very limited quantities has hindered evaluation of the mechanical 

properties of BNNTs as reinforcing agents for structural materials. A recurrent issue is that the 

synthesis of SWNTs requires processing temperatures in excess of 3000°C and low pressures

(ref. 12). The formation of BNNTs was only predicted in 1994, initial synthesis of MWNTs by 

arc discharge occurred in 1995, and refinement of the method resulted in the production of 

DWNTs and SWNTs in 1996 (ref. 13). In recent years, the yield of MWNTs has reached the 

grams level, but the mass production of high-purity, low-defect SWNTs remains a challenge. 

Previous work suggests that nanotube diameter will govern the strength and stiffness of BNNTreinforced composites (ref. 14). Fewer walls or shells translates to a higher nanotube aspect 

ratio, which will be critical for capitalizing on the exceptional properties in bulk product. It is 

evident that the efficient synthesis of large quantities will be necessary for BNNTs to be utilized 

in large structures.
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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2. Candidates for Processing of BNNTs

2.1. Incumbent Synthesis Techniques

Initial BNNT synthesis methods were adapted from CNT equivalents, but dedicated methods 

have been developed. A variety of synthesis techniques have been successfully employed, 

including chemical vapor deposition (CVD), reactive ball milling, laser ablation, and arc 

discharge (refs. 2 and 3). The lower-temperature methods, such as CVD and ball milling, tend to

result in larger quantities than high-temperature methods, but MWNTs dominate and the 

impurity/defect levels are high. A leading candidate among the low-temperature synthesis 

techniques is the boric oxide chemical vapor deposition (BOCVD) method (ref. 15). BOCVD is 

capable of synthesizing well-crystallized MWNTs of high purity. BNNT growth occurs within 

an induction furnace with a large temperature gradient (fig. 3). An equi-molar mixture of B and 

MgO is evaporated to produce B2O2 gas and Mg vapor, the latter acting as a floating zone 

catalyst. These precursors are then transported with an Ar carrier gas into a reaction chamber 

fabricated from boron nitride (BN). Introducing ammonia gas (NH3) results in the formation and

deposition of BNNTs on the wall of the chamber. The conversion rate from B to BN is

approximately 40% using this processing route. The synthesis reactions which occur involve

equations of the following form:

2(B)solid + 2(MgO)solid => (B2O2)gas + 2(Mg)gas (1)

and

(B2O2)gas + 2(NH3)gas => 2(BN)solid + 2(H2O)gas + (H2)gas (2)

Figure 3. BOCVD method for synthesizing BNNTs (ref. 12).

BNNTs synthesized via this route tend to possess relatively large diameters of ~50–80 nm, and 

current efforts aim to reduce nanotube diameters to the sub-10 nm scale (ref. 4). Other 

shortcomings of this approach are that the reagents can be dangerous, and the deposited product 
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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is full of defects, e.g. regions of crystallographic disorder. It transpires that high-temperature 

synthesis techniques may be the best candidates for high-quality SWNT production. Methods 

such as laser ablation and arc discharge do produce low-defect BNNTs, but in relatively small 

quantities. Figure 4 outlines the fundamental aspects of high-temperature processing methods 

used to generate large fractions of SWNTs (ref. 16). A solid precursor, often a consumable 

cathode, is vaporized and combined with reactive gases. The final product emerges during 

controlled cooling in the presence of a catalyst.

Figure 4. Concept behind most high-temperature processing methods (ref. 16).

A promising technique which employs this concept is referred to as the pressurized vapor/

condenser (PVC) method (ref. 17). This modified laser ablation approach has been championed 

in a combined effort involving Jefferson Lab, the National Institute of Aerospace, and NASA

LaRC (JL/NIA/LaRC). Essentially, a 5 kW-class CO2 laser is used to progressively evaporate a 

boron target inside a vertically mounted chamber. This produces an upward stream of hot boron 

vapor (~4000 °C) in a high-pressure atmosphere (~1 MPa) of nitrogen gas. A wire traversing the 

stream of gas acts as a physical catalyst for the ensuing reaction. Condensation of the boron 

vapor forms liquid boron droplets which serve as nucleation sites for the growth of BNNT 

networks that interlock to form fibrils (fig. 5a). The typical output is ~1 mm diameter by 3 cm 

long yarns comprised of highly crystalline, small-diameter BNNTs (fig. 5b). In addition to the 

limited quantities produced (~40 mg/hr), a major limitation is that purity is still an issue as the 

yarns contain significant amounts of amorphous and other BN phases (ref. 2). The synthesis 

reaction which occurs involves an equation of the following form:

2(B)solid + (N2)gas + Ar => 2(BN)solid + Ar (3)
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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Figure 5. Pressurized vapor/condenser method; (a) Schematic of JL/NIA/LaRC PVC 

technique for synthesizing BNNTs; (b) Typical BNNT yarn produced using

the PVC approach (ref. 17).

Although the PVC method is compatible with mass production of BNNTs, the use of a 

consumable target restricts production to batch processing. Another promising high-temperature 

method is arc discharge or thermal plasma processing, which avoids the use of consumable 

targets (ref. 3). However, the most common techniques still use consumable electrodes to 

generate the plasma (also a potential source of contamination). Typically, the approach involves 

vaporization of solid or liquid suspension precursors in a hot, ionized gas and the subsequent 

condensation of nano-sized particulates (ref. 16). Traditionally, the plasma-forming gas is inert, 

solely provides the heat source, and does not contribute to the composition of the sprayed 

product. In contrast, the injection of a reactive gas or liquid can be used to create in-situ

chemical reactions with solids in the plasma plume. This approach is known as plasma-chemical 

processing, and is used to produce large quantities of a wide variety of nano-materials (ref. 18).

2.2. Direct Current (DC) Plasma Synthesis

Among arc discharge techniques, the DC thermal plasma process is most commonly applied to 

nano-material production. Essentially, an arc between two highly charged electrodes creates a 

hot ionized gas plume and the cathode is steadily consumed. In the direct method, the nozzle is 

neutral and the target is the anode. In the non-direct method, the nozzle becomes the annular 

anode (fig. 6) (ref. 20). [Traditionally, both processes are conducted under ambient conditions, 

and nano-material synthesis takes advantage of the inert gas shroud typically created.] Classified 

as high-velocity, low-volume techniques, high-purity CNTs have been synthesized via either

process using carbon electrodes/targets (ref. 18). Experience shows that the yield is much higher 

via the non-direct approach because it represents a departure from batch processing.
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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Significantly, consumable electrode plasma techniques do not lend themselves readily to the 

synthesis of BNNTs. Electrodes made from either B or BN do not possess sufficient electrical 

conductivity to support an arc unless doped (or sheathed) with metals (ref. 2). Consequently, 

significant amounts of metallic impurities are transferred to the final product. This has led 

researchers to explore alternative plasma synthesis methods for the production of BNNTs. Slave 

BN rods have been evaporated indirectly during arc discharge processing, but the use of refined

feedstock has proved to be more efficient (ref. 12). These precursors are typically transported to 

the reaction zone in fluid form (gas or liquid). What follows are examples of DC plasma

methods employing different types of feedstock, and the precursors being injected at varying 

locations.

Figure 6. DC plasma process with reaction occurring outside the discharge zone; 

(a) Transferred arc torch, using solid precursors as the target; (b) Nontransferred arc torch, using radial injection of solid precursors (ref. 20).

Basic DC non-transferred arc systems operate under atmospheric pressure and involve the 

injection of plasma forming gases circumferentially around a consumable cathode with 

additional reactants being introduced outside the discharge zone (fig. 6b) (ref. 20). Such systems 

have been modified to incorporate the injection of additional liquid precursors radially through 

the anode, i.e. inside the discharge zone (fig. 7) (ref. 21). This approach also allows atomized 

liquid compounds or particle/liquid suspensions to be introduced into the plasma. Other systems 

have been modified for the injection of solid precursors radially through the anode (fig. 8) (ref. 

22). This permits powders transported by a carrier gas or liquid to be introduced directly into the 

discharge zone.
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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Figure 7. DC plasma process using radial injection of liquid precursors, and reaction 

occurring inside the discharge zone (ref. 21).

Figure 8. DC plasma process using radial injection of solid precursors, and reaction 

occurring inside the discharge zone (ref. 22).
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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Thermal decomposition of powder feedstock starts from the powder surface and then propagates 

toward the powder interiors when using arc discharge or thermal plasma techniques (ref. 21). If 

the residence time in the high-temperature zone is not sufficient, the central regions of the 

particles are only partially processed. Partial conversion of particles can result in the break-up of 

the crystals and the formation of micro-crystals and amorphous phases. The dwell time in the 

plasma plume has been extended by attaching so-called “reaction chambers” to the exit nozzle of 

the plasma gun (ref. 18). Expanding the hot zone allows the desired transformations, 

conversions or chemical reactions to reach completion.

In figures 7 and 8, the precursors are injected at the location of plasma formation and chemical 

reactions occur inside the discharge zone. However, figure 6 indicates that some of the reactants 

can be introduced at the exit nozzle or beyond, such that synthesis occurs outside the discharge 

zone. The plasma forming gas, which is typically inert, is introduced separately and only 

provides the initial heat source. The subsequent injection of reactive solid, liquid, or gaseous 

precursors leads to less fouling of the arc chamber (ref. 24). Increased flexibility and careful

control of cooling rates are benefits of this approach. 

Figure 9 shows an early example of the application of the “outside the discharge zone” concept 

to the production of BNNTs (ref. 18). The non-transferred DC plasma process is contained 

within a reactor vessel operating at atmospheric pressure (ref. 25). A tungsten (W) cathode and 

annular copper (Cu) anode create the plasma arc using an Ar/N2 mixture as the forming gas. The 

Ar and N2 flow rates are 45 standard liters per minute (slpm) and 2 slpm, respectively. When 

ionized, the atomic nitrogen becomes the reactive precursor, which combines with the solid 

precursor injected radially at the torch exit nozzle. The synthesis reaction involved in this 

processing route utilizes an equation of the following form:

(BN)hexagonal [+ Ni + Y] + N2 + Ar => (BN)nanotube + N2 + Ar (4)

The reactants consist of 1 μm BN powder mixed with Ni/Y powders (atomic ratio 9:1) as 

catalysts. The reactant mixture is introduced into the formed plasma using Ar carrier gas at the 

carbon cylinder adjacent to the nozzle exit. The remaining stack of carbon cylinders serve to 

extend the hot zone to enhance the reaction. The end product comprises a gray deposit on the 

reaction chamber walls that contains BNNTs. This method is appealing because synthesis is 

based on a simple physical transformation of BN, the allotropic transition occurring in the 

presence of excessive nitrogen gas. Also, the length of the hot zone can be adjusted by choosing 

the number of reaction cylinders attached (ref. 25). The deficiencies of this approach are that the 

product has to be forcibly removed, the catalysts become impurities, and contamination will 

result from erosion of the W and Cu electrodes.
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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Figure 9. DC plasma process using radial injection of solid precursors, and reaction 

occurring outside the discharge zone (refs. 18, and 25).
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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2.3. RF Thermal Plasma Synthesis

When using DC plasma methods, the final product always suffers from the metallic impurities 

introduced by a consumable cathode. However, the semi-continuous nature of the process does 

offer hope for mass production which has lead researchers to investigate RF plasma methods. 

This thermal plasma technique is an electrodeless process, which uses inductive coupling to 

ionize an inert gas (ref. 19). Processing is conducted within an ultra-clean vessel, operating 

under a partial-pressure, inert gas atmosphere. In contrast with DC plasma techniques, it is 

classified as a low-velocity, high-volume technique and is free from contamination resulting 

from cathode erosion. In RF plasma torches, gaseous, liquid, or solid precursors can be injected 

axially, as opposed to radial injection in DC plasma torches (fig. 10). A carrier gas transports the 

precursors down an injection probe, which introduces the reactants in the middle of the plasma. 

On the Tekna RF torch shown, the central gas forms the plasma and the cooler sheath gas 

protects the confinement tubes. The characteristically high temperatures extending along the 

torch centerline permit evaporation of even the highest boiling point materials (ref. 26). The rate 

of chemical reaction is also enhanced by the long residence time in the very hot zone (ref. 20). 

The process is already being used for the synthesis of large quantities of high-purity, highlycrystalline product using a variety of precursors (ref. 5).

Tekna Plasma Systems, Inc. (Sherbrooke, Quebec, Canada) is the industry leader in RF plasma 

torch design/manufacture, and is also an industry leader in the commercial production of nanopowders via induction plasma synthesis (fig. 11) (ref. 5). The lack of consumable electrodes or 

targets allows for continuous, rather than batch, processing. The commercial scale of the 

operation is evident in figure 11a. The 400 kW installation produces 20–40 kg/h, depending on 

the nature of the feedstock and the degree of spheroidization required. The equipment set-up 

shown in figure 11b illustrates the self-contained nature of the process (ref. 51). The schematic 

in figure 11c outlines the processing details and shows the three collection points for 

progressively finer powder (at the bottom) (ref. 27). The typical operating parameters shown in 

figure 11d reveal the 5:1 ratio between sheath and central gas for effective confinement of the 

plasma plume.

It is important to note that Tekna currently produces nano-materials, which do not include NTs. 

However, the production concepts are directly applicable to the synthesis of large quantities of 

high-purity BNNTs. Tekna continues to evolve RF gun manufacturing and holds patents for a 

broad range of RF plasma processing technologies, including product collection and separation 

devices (ref. 19). Recently, RF technology championed by Tekna has produced significant 

quantities of CNTs at the University of Sherbrooke, Canada (ref. 29). The very high 

temperatures inherent to the process promote the allotropic transformation of carbon black 

powder into SWNTs using an Ar/He plasma in the presence of a mixture of metallic catalysts.

The synthesis reaction involved in this processing route involves an equation of the following 

form:

(C)solid [+ Ni + Co + Y2O3] + (Ar)gas + (He)gas => (C)nanotube + (Ar)gas + (H2)gas (5)
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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Figure 10. Characteristics of RF torches manufactured by Tekna Plasma Systems, Inc.;

(a) Construction schematics; (i) PL-50 torch body; (ii) the inner workings (ref. 

23); (b) Typical thermal profiles [calculated]; (i) PL-50; (ii) PL-70 (ref. 26).
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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Figure 11. Tekna Plasma Systems, Inc.; (a) Industrial facility for spheroidization of bulk 

powder (ref. 5); (b) Induction plasma installation for nanopowders synthesis 

(inert environment) (ref. 28); (c) Schematic of equipment supporting RF torch 

operation (ref. 27); (d) Typical settings for a Tekna PL-35 torch (ref. 27).

Figure 12b shows the prototype reactor designed for the mass production of CNTs (ref. 29). The 

Tekna RF plasma torch has a five-turn induction coil, which is energized by a 40 kW Lepel

power supply. Typically, SWNT synthesis is conducted at a fixed plate power of 40 kW, an 

operating frequency ~3 MHz, and a constant chamber pressure of ~66 kPa. During stable 

operation, the sheath gas (He) is maintained at a constant flow rate of 120 slpm, the central gas 

(Ar) is supplied at 25 slpm, and the powder carrier gas (Ar) is injected at 5 slpm. Powder

feedstock is delivered axially by the probe at feed rates of 72–120 g/h. Extensive mathematical 

modeling, validated by enthalpy probe and calorimetric measurements, has permitted the 

temperature profile and fluid flow in the plasma plume to be characterized (fig. 12a) (refs. 30 and 

31).
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Figure 12. University of Sherbrooke; (a) Mathematical modeling of temperature profile 

during CNT synthesis; (b) Schematic of apparatus used for RF plasma 

processing of SWCNT sheets; (c) Typical characteristics of product (ref. 29).

It is worth studying the anatomy of this system in more detail because it provides useful 

guidelines for the current effort (fig. 13). The reaction chamber is a double-walled cylindrical 

tube with the primary purpose of providing a suitable environment for the formation and growth 

of CNTs. The chamber contains interchangeable graphite inserts for flexible control of 

processing temperature and cooling rate. The quenching chamber comprises a double-walled 

cylindrical segment, which provides a region for the completion of SWNT growth and for the 

initiation of secondary chemical reactions. The chamber is equipped with multiple ports for 

injection of chemical agents for in-situ purification or functionalization. The cylindrical 

filtration chamber contains tubular porous metallic filters, which separate the solid SWNTcontaining materials from the residual gases.

This research activity continues and employs a similar Tekna RF plasma torch to that installed in 

the LaRC facility. The design of the system and the precursors injected also bear a striking 

resemblance to pioneering Russian work in this arena (ref. 32). A shortcoming of this approach 

is that the graphite inserts would become a source of contamination during BNNT synthesis. In 

addition, the tubular filter system limits the process to batch quantities and is not compatible with 

mass production. However, the process could be readily adapted to the synthesis of BNNTs at 

LaRC by replacing the reaction and quenching chambers with the very large chamber (fig. 14). 

The throw distance is very long, and plume length can be controlled by the ambient chamber 

pressure. The extent of both the hot zone and the cooling zone could potentially be controlled in 

free flight. In addition, the filter system could be replaced by a cyclone separator to facilitate 

semi-continuous production.
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Figure 13. Significant features of University of Sherbrooke apparatus; (a) Construction 

of synthesis chambers; (b) CNT collection unit geometry (ref. 29).

Figure 14. Potential replacement of sequential reaction/quenching chambers; (a) LaRC 

facility; single 1 m diameter x 1 m long chamber; (b) Tekna facility; dual 0.4 

m diameter x 0.5 m long chambers (ref. 5).
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2.4. RF Plasma-Chemical Synthesis

In the 1980s, the Russian nuclear industry championed RF plasma-chemical synthesis of very 

fine powders of metallic carbides and nitrides (refs. 24 and 32). The reactions were promoted 

either inside or outside of the plasma discharge zone, and the reactants were in the solid, liquid,

or gas phase. In summarizing the extensive research effort, the processing permutations of 

significance to the LaRC effort are listed below.

2.4.1. Silicon Carbide Nano-powders Produced Inside the Plasma Discharge Zone

The synthesis reaction adopted in this approach involves an equation of the following form:

(SiO2)solid + (CH4)gas + (Ar)gas + (H2)gas => (SiC)solid + (H2O)liquid + (Ar)gas + (H2)gas (6)

Figure 15 shows a schematic of the RF plasma reactor used to convert a solid metal oxide (SiO2) 

into a solid metal carbide (SiC) (ref. 24). The reaction occurred in the presence of reactive gas, 

such as methane (CH4), and without evaporation of the precursor powders. The reagents were 

injected axially (SiO2 + H2) and radially (CH4 + Ar) into the torch and the reaction occurred 

inside the discharge zone. Note that additional H2 was introduced into the zone to prevent 

carbon deposition on the inductor walls. The RF torch operated at a discharge power of 9.2 kW,

and SiO2 was injected at a rate of 45 g/min. The gas flow rates comprised 1.1 slpm for CH4, 17 

slpm for Ar, and a total of 17 slpm for H2 (including carrier gas). Upon exiting the nozzle, the 

end product entered a quenching chamber and was collected in a filtration device. The SiC 

particulate produced was 40–150 μm in diameter and the degree of conversion from SiO was 

approximately 100% using this processing route.

2.4.2. Titanium Nitride Nano-powders Produced Outside the Plasma Discharge Zone

The synthesis reaction adopted in this approach involves an equation of the following form:

(TiCl4)gas + 2(H2)gas + 1/2(N2)gas => (TiN)solid + 4(HCl)gas (7)

Figure 16 shows a schematic of the RF plasma reactor used to produce metal carbides and 

nitrides (including BN) from metal chlorides (ref. 32). In essence, a liquid metal chloride (TiCl4) 

was vaporized in the presence of reactive gases such as N2 and H2 or ammonia (NH4). The 

ensuing gas-phase synthesis reaction produced a solid metal nitride and gaseous by-product. Ar 

was simply the inert plasma forming gas, and the reaction occurred outside the discharge zone. 

This approach thereby avoided any deposits forming within the plasma gun and allowed for more 

continuous operation. Only Ar was injected into the torch, and the reagents (TiCl4 + N2 + H2) 

were subsequently introduced radially at the exit nozzle. The conversion reaction occurred 

between the evaporated liquid and the dissociated gases downstream of the torch. The TiN 

particulate produced was 10–50 nm in diameter, and the degree of conversion from TiCl4 was 

approximately 80% using this processing route.
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Figure 15. RF plasma process using axial injection of solid and gaseous precursors, 

with reaction occurring inside the discharge zone (refs. 24, and 32).

Figure 16. RF plasma process using radial injection of liquid and gaseous precursors, 

with reaction occurring outside the discharge zone (refs. 24, and 32).
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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3. Proposed LaRC RFPS Approach

3.1. Processing Philosophy

The phase diagram for boron nitride is of particular relevance to the allotropic transformation

(thermal plasma) approach. Complete versions have been compiled for pure carbon and pure 

boron, but only partial versions are currently available for BN (fig. 17) (refs. 11, 34, and 35). It 

is recognized that the extreme pressures cited in these studies are not necessarily compatible with 

an atmospheric RF plasma spray system. However, establishing pressure-temperature (P vs. T)

diagrams indicating the phase field where NT formation is prevalent in the appropriate pressure 

regime could be beneficial. Computational modeling will undoubtedly aid in reducing the scope 

of the experimental matrix by tightening the boundaries (refs. 30 and 31). Process simulation 

will allow correlation of control settings with P and T, and define the relationship with product 

quality. The objective would be to identify the P vs. T regime in which high-purity, low-defect, 

and small-diameter BNNTs are produced. The development of such a thermodynamic phase

diagram would be an important consideration for any proposed research.

Figure 17. Pressure vs. Temperature phase diagrams; (a) pure carbon (ref. 34); (b) pure 

boron (ref. 35); (c) boron nitride (ref. 36).
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Previous BNNT processing work has shown that lower temperature processing tends to produce 

large diameter MWNTs which are laden with defects (ref. 3). It is accepted that effective 

production of SWNTs requires the combination of very high temperatures with low pressure. 

Researchers have demonstrated that the higher the growth temperature, the better the reactions 

necessary for crystallization occur and the fewer the defects (ref. 2). It is also possible to 

customize the synthesis recipe to promote the formation of BNNTs with a specified crystal 

structure and morphology. In this work, the critical temperatures for RFPS synthesis of BNNTs 

are the sublimation point of BN (2973°C) for thermal plasma processing, and the vaporization 

point of B (3927°C) for plasma-chemical processing (refs. 13 and 35). Very hightemperature/partial-pressure RF plasma techniques have already been used to produce highpurity, single-walled CNTs (ref. 29). However, it is recognized that there is a disadvantage to 

this synthesis approach. The nanotube length is typically rather short due to the spraying action 

characteristic of the process (ref. 33). In this effort, it is anticipated that what the final product 

may lack in NT length will be more than compensated for by the purity, consistency, and lack of 

defects.

3.2. Characteristics of the Facility

The LaRC RFPS facility was originally procured to process high-melting point, highly-reactive 

metallic materials into thin gages and/or fiber-reinforced composites. More recent applications

of RF plasma spray processing has included;

 thin–gage, difficult-to-process materials: γ-titanium aluminide foils for thermal protection 

system applications on launch vehicles (ref. 37)

 metal coated glass fabric: porous fiber/metal preforms for hybrid laminate materials (refs. 

38 and 39)

 metal coated textiles: metallic filigrees of copper for lightning protection

 multi-metal coated carbon fabric: functional layers of tantalum, copper, and titanium for 

radiation protection (Z-shielding) (ref. 40)

Figure 18a illustrates the main features of the RFPS facility at NASA LaRC. The apparatus

consists of a horizontally-mounted, water-cooled cylindrical chamber with a water-cooled, 

rotating/translating mandrel (fig. 18b). The static RF torch is vertically-mounted on the 1-meter

diameter by 1-meter long chamber. The system is driven by a 240 kVA Lepel generator, with a 

maximum output of 100 kW and tunable oscillator frequencies of 150–450 kHz. The system 

consists of five independent mass flow meters which allow up to 850 slpm of inlet gases. 

Powder feed rates can be carefully controlled between 1 and 100 g/min, and typical particle size 

is 75–125 μm. Typically, a mixture of Ar and He is used as a plasma-forming gas for generating 

temperatures up to 3000°C. A partial pressure of H2 is introduced (up to 4% by volume) in order 

to create much higher plasma temperatures. The operating parameter ranges for the RFPS 

facility are;

 low pressure = 7–100 kPa

 low velocity = 10–100 m/s

 extended spray distance = 150–600 mm

 long residence time = 10–25 ms
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Figure 18. Radio frequency plasma spray facility located at NASA LaRC; (a) Features of 

the processing unit; (b) Deposition on fabric-wrapped mandrel.

3.3. Facility Modifications for BNNT Synthesis

In order to transition from an old plasma gun designed for the spraying of metals, several 

upgrades to the LaRC RFPS facility were deemed necessary. The first was to replace the mass 

flow controllers for the gaseous precursors in order to increase the flow rate capability (fig. 19a). 

Second, the ability to contain potentially hazardous products using a hydrostatic precipitator was 

paramount for operational safety (fig. 19b). The improved gas management system will allow 

for careful control of an increased volume of inlet gases. An upgrade of the exhaust filtering 

system was considered to be critical. The new high-volume exhaust system, including 

hydrostatic precipitator, will permit effective handling of any toxic outlet gases and by-products. 

Third, a new plasma torch, manufactured by Tekna, was installed (fig. 20). In contrast to the old 

torch manufactured by (now defunct) Praxair/TAFA Corp., this provides ready access to spare 

parts and technical support from an active vendor.

Figure 19. Gas control in LaRC RFPS facility; (a) Inlet gases; (b) Outlet gases.
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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Figure 20. Tekna RF plasma torch; (a) Anatomy of a typical torch (refs. 23, and 30); (b) 

Adjustable height axial injection probe (ref. 19); (c) Modular installation of 

PL-70 torch at LaRC.

Figure 20a illustrates the anatomy of a typical RF torch manufactured by Tekna Plasma Systems, 

Inc. The torch assembly consists of three basic components; the induction coil, the plasma 

confinement tube(s), and the gas distribution head. The LaRC PL-70 has a 7-turn coil and can be 

operated up to an induction power of 100 kW. The outer and inner confinement tubes are 

fabricated from silicon nitride and quartz, respectively. The gas distributor is responsible for the 

injection of different gas streams into the discharge zone. The outermost sheath gas is 

introduced in a manner that produces a helical or straight flow and is responsible for protecting 

the confinement tube. The central gas is introduced in such manner as to cause a swirling action 

and is responsible for forming the plasma. The carrier gas is introduced via an injection probe 

located at the center of the torch head. Multiple choices for both gas composition and flow rates 

allow for a great deal of flexibility and permit a broad spectrum of processing conditions. The 

probe allows solid, liquid, or gaseous precursors to be introduced axially with the carrier gas. 
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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The height of the injector within the discharge zone is readily adjustable (fig. 20b). The torch 

design is modular so that the installation can be removed for periodic maintenance (fig. 20c).

In addition, retraction of the mandrel apparatus will facilitate free-flight plasma processing of 

precursors by increasing the residence time in the hot zone (fig. 21a). Plus, auxiliary access

ports through the chamber wall are available for collection/separation/fractionation of free-flight 

sprayed product (fig. 21b). One objective will be to devise an effective means of isolating 

BNNTs from the by-products, and also dividing them based on architecture. Some consideration 

of the devices available for capturing fine particulate is pertinent for the continuous production 

of BNNTs. These may include cyclonic and electrostatic separators or combinations thereof, 

which have been successfully applied to nanoparticle collection (fig. 22) (refs. 41 and 42). For 

example, an industrial unit based on the concept shown in figure 22a, has a processing capacity 

of 20-40 kg/h for ultrafine, spheroidized powders (ref. 5).

Figure 21. Important features of LaRC RFPS facility; (a) Mandrel retraction to permit 

free-flight synthesis; (b) Chamber interior showing auxiliary access ports.

3.4. Experimental Methodology

3.4.1. Thermal Plasma Processing

The projected processing path involves decomposition of h-BN powders to form dissociated 

gases already with the correct stoichiometry, followed by recombination to form BNNTs. The 

simplest route is to take a BN precursor and induce an allotropic transformation using hightemperature plasma at a specified pressure (ref. 36). The BN needs to be vaporized and then 

encouraged to form BNNTs on cooling, hopefully in the absence of a catalyst. If successful, this 

would yield a product of extreme cleanliness because of the lack of reactive species and the 

deliberate introduction of contaminants. In this case, the projected synthesis reaction will follow

an equation of the form below:

(BN)hexagonal+ Ar + He + H2 => (BN)nanotube+ Ar + He + H2 (8)
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Figure 22. Candidate continuous collection devices for LaRC RFPS facility; (a) High 

volume cyclone separation concept (ref. 41); (b) Principle behind high 

volume electrostatic drum separators (ref. 42).
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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3.4.2. Plasma-Chemical Processing

The projected processing path involves vaporization of B powders, combination with dissociated 

nitrogen gas with 1:1 stoichiometry, followed by an in-situ chemical reaction to form BNNTs. 

The more complicated route is to take a B precursor and combine it with reactive species outside 

of the discharge zone. This approach may produce a more reliable product in a more controlled 

manner. Dwell times, temperatures, and gas compositions can be monitored and adjusted for 

maximum yield, consistency, or aspect ratio. It is possible to use a suspension probe such that 

the metallic powder precursor can be introduced in fluid form, i.e. very fine particulate

suspended in a medium. The downside of this methodology is the possibility of organic 

contamination. In this case, the projected synthesis reaction will follow equations of the form 

below:

2 (B)solid+ (N2)gas+ (H2)gas + Ar + He => 2(BN)nanotube+ (H2)gas + Ar + He (9)

or

2(B)solid+ 2(NH3)gas+ Ar + He => 2(BN)nanotube+ 3(H2)gas+ Ar + He (10)

3.4.3. Manageable Experimental Matrix

The combination of implementing two fundamentally different approaches and having many 

permutations for the processing parameters dictates the formulation of a manageable test plan. 

The underlying experiment is to vary the plasma temperature and the operating pressure. The 

many equipment settings governing these process variables include, but may not be restricted to

the following:

 Feedstock = high-purity, 30-50 μm diameter B or h-BN powders

 Induction power and frequency

 Gas flow rates

 Carrier / Central / Sheath gas balance

 Argon (Ar) / Helium (He) / Hydrogen (H2) balance

 Substitution of Nitrogen (N2)

 Injection probe position (inside vs. outside discharge zone)

3.5. Projected Outcome

In the prior Russian work, most plasma conversion processes were conducted outside the 

discharge zone, so that only the inert, plasma-forming gas was inductively heated. The

advantage to introducing reactants downstream of the plasma torch was that the deposition of 

conductive products within the discharge chamber was avoided. Experience revealed that such 

deposits progressively prevented effective coupling of the RF inductor with the reactive 

precursors and inhibited plasma formation. In this case, neither B nor BN are classified as 

conductive products, which does create the opportunity for plasma synthesis inside the discharge 

zone. However, any deposits within the chamber will impact torch performance, rendering this 
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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25

approach less attractive. In addition, many of the plasma-chemical synthesis techniques are not 

very appealing because dangerous by-products, such as hot hydrochloric acid, tend to be 

involved. Consequently, if thermal plasma synthesis alone is effective either inside or outside 

the discharge zone, then proceedings will be greatly simplified. RFPS technology readily lends 

itself to very high-processing temperatures and high-purity product. The objective of designed 

experiments will be to identify the parameters promoting the synthesis of low-defect, smalldiameter BNNTs. In light of historical processing difficulties, production of large quantities of 

high-purity BNNTs with any architecture or aspect ratio may be considered a bonus.
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

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4. Concluding Remarks

The projected advantages of using the LaRC RFPS facility for the synthesis of large quantities of 

high-purity BNNTs may be summarized as follows:

Problem: Synthesis of high-quality BNNTs requires much higher temperatures than CNTs

 (> 4,000°C).

Solution: Use inductively-coupled (RF) plasma which has a temperature capability of ~

12,000°C.

Problem: Incumbent arc discharge processes are low-volume, high-velocity processes; radial 

powder feed, short dwell times.

Solution: RF plasma is a high-volume, low-velocity process; axial powder feed, long residence 

time (+ adjustable plume length and powder injector height).

Problem: Incumbent methods are batch processes (not compatible with mass production).

Solution: RFPS is a semi-continuous process which is readily scalable.

Problem: Impurities result from consumable electrodes/targets and catalysts.

Solution: RF plasma processing uses no electrodes or targets (and may avoid catalyst usage).

Problem: Handling of end product can be hazardous, e.g. pyrophoric, asbestosis.

Solution: Entire RF plasma process occurs within a self-contained, inert gas environment.
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(BNNTs) for Structural Applications: Part I

31

Appendix A.

Prior to the publication of this White Paper, details concerning work being performed at the 

National Research Council - Canada (NRC-C) emerged (ref. 43). Evidently, this effort is an 

extension of an earlier campaign to mass produce CNTs (fig. A-1), accompanied by extensive 

modeling of RF plasma synthesis of NTs (refs. 44, 45 and 46). The current activity involves the 

allotropic transformation of h-BN powder into high quality BNNTs in the presence of a hydrogen 

catalyst. Although only a partial processing recipe is accessible, it is apparent that the approach is 

very successful at producing large quantities. A 60kW RF induction plasma torch generates 

plasma temperatures > 7,700°C, causing dissociation of the reactants. Subsequently, a controlled 

thermal gradient between ~ 3,700°C and ~ 2000°C causes BNNT growth in a reaction chamber. 

The RF torch is coupled to a ~ 1 m long by ~ 20 cm diameter, ceramic-lined reactor maintained at 

~ 720 torr. Best results are obtained when the plasma-forming gas is a ternary mixture of Ar, N2,

and H2, and the powder feedstock is pure h-BN, injected at a rate of 0.5-1.0 g/min.

Figure A-1. Prototype RF plasma reactor developed for synthesis of CNTs (ref. 45).
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

(BNNTs) for Structural Applications: Part I

32

The NRC-C group subscribes to the “root-growth model” for BNNT formation in the current 

work (ref. 47). The sequence of BNNT growth during the RF processing is cited as consisting of 

the following:

 Vaporization of BN source

 Decomposition of BN vapors into boron and nitrogen

 Formation of nano-sized boron droplets

 Reaction between boron nanoparticles and nitrogen

 Growth of BNNT from boron nanoparticles

Based on this proposed sequence of events, the synthesis reaction involves equations of the 

following form:

(BN)hexagonal [+Ar + N2 + H2] => (B)gas+ (N)gas [+Ar + N2 + H2] (11)

and

(B)gas+ (N)gas [+Ar + N2 + H2] => (B)liquid+ (N)gas [+Ar + N2 + H2] (12)

and

(B)liquid+ (N)gas [+Ar + N2 + H2] => (BN)nanotube [+Ar + N2 + H2] (13)

A mixture of “candy cotton-, fibril-, and cloth-like” material was produced at a rate of 10–20 g/h, 

and the wispy material could be readily finger-twisted into > 20 cm long yarns (ref. 43). 

Analysis revealed that all of the materials consisted of few-walled BNNTs (< 10 nm in 

diameter). However, the product purity via the method described was ~65%, with the balance 

comprising ~25% BN-derivatives and ~10% amorphous B particles. Consequently, there are 

opportunities for LaRC activities to improve upon the NRC-C effort by using process 

diagnostics, statistically designed experiments, and even to develop a phase diagram. The 

emphasis of synthesis activities will shift toward adjusting these ratios and maximizing the purity 

of the end product. The incumbent method may employ a friable liner for the narrow reaction 

chamber which may be a source of contamination, and free-flight synthesis in a wide-open 

chamber may be a benefit. An additional LaRC objective may be the RFPS deposition of metals 

on to NRC-generated BNNT material, followed by VARTM processing, in order to produce 

hybrid laminate composites (refs. 37 and 38). However, there is considerable work remaining if 

the mechanical properties of the end product are even going to approach theoretical values (table 

A-1) (refs. 43, 48, and 49). Lastly, research on collection devices for in-situ nanotube separation 

and alignment may prove most useful in this endeavor, e.g. the utilization of cyclonic, 

electrostatic and/or spooling separator technologies (refs. 40, 41, and 50).
Radio Frequency Plasma Synthesis of Boron Nitride Nanotubes

(BNNTs) for Structural Applications: Part I

33

Table A-1. Comparison of mechanical properties of boron nitride- and carbon-based 

materials (refs. 43, 48, and 49).
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It is evident that nanotubes, such as carbon, boron nitride and even silicon, offer great potential for many aerospace applications. The opportunity exists to 

harness the extremely high strength and stiffness exhibited by high-purity, low-defect nanotubes in structural materials. Even though the technology associated 

with carbon nanotube (CNT) development is mature, the mechanical property benefits have yet to be fully realized. Boron nitride nanotubes (BNNTs) offer 

similar structural benefits, but exhibit superior chemical and thermal stability. A broader range of potential structural applications results, particularly as 

reinforcing agents for metal- and ceramic-based composites. However, synthesis of BNNTs is more challenging than CNTs mainly because of the higher 

processing temperatures required, and mass production techniques have yet to emerge. A promising technique is radio frequency plasma spray (RFPS), which 

is an inductively coupled, very high temperature process. The lack of electrodes and the self-contained, inert gas environment lend themselves to an ultraclean 

product. It is the aim of this White Paper to survey the state of the art with regard to nano-material production by analyzing the pros and cons of existing 

methods. The intention is to combine the best concepts and apply the NASA Langley Research Center (LaRC) RFPS facility to reliably synthesize large 

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Boron nitride nanotubes; Inductively-coupled plasma; Materials engineering; Nanocomposites; Processing and synthesis

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