Boron nitride

Last updated
Boron nitride
Hbncrystals.jpg
Names
IUPAC name
Boron nitride
Identifiers
3D model (JSmol)
ChEBI
ChemSpider
ECHA InfoCard 100.030.111 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 233-136-6
216
MeSH Elbor
PubChem CID
RTECS number
  • ED7800000
UNII
  • InChI=1S/BN/c1-2 Yes check.svgY
    Key: PZNSFCLAULLKQX-UHFFFAOYSA-N Yes check.svgY
  • InChI=1S/B2N2/c1-3-2-4-1
    Key: AMPXHBZZESCUCE-UHFFFAOYSA-N
  • InChI=1S/B3N3/c1-4-2-6-3-5-1
    Key: WHDCVGLBMWOYDC-UHFFFAOYSA-N
  • InChI=1/BN/c1-2
    Key: PZNSFCLAULLKQX-UHFFFAOYAL
  • B#N
Properties
BN
Molar mass 24.82 g/mol
AppearanceColorless crystals
Density 2.1 g/cm3 (h-BN); 3.45 g/cm3 (c-BN)
Melting point 2,973 °C (5,383 °F; 3,246 K) sublimates (c-BN)
Insoluble
Electron mobility 200 cm2/(V·s) (c-BN)
1.8 (h-BN); 2.1 (c-BN)
Structure
Hexagonal, sphalerite, wurtzite
Thermochemistry
19.7 J/(K·mol) [1] [2]
Std molar
entropy
(S298)
14.8 J/K mol [1] [2]
−254.4 kJ/mol [1] [2]
−228.4 kJ/mol [1] [2]
Hazards
GHS labelling:
GHS-pictogram-exclam.svg
Warning
H319, H335, H413
P261, P264, P271, P273, P280, P304+P340, P305+P351+P338, P312, P337+P313, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 0: Exposure under fire conditions would offer no hazard beyond that of ordinary combustible material. E.g. sodium chlorideFlammability 0: Will not burn. E.g. waterInstability 0: Normally stable, even under fire exposure conditions, and is not reactive with water. E.g. liquid nitrogenSpecial hazards (white): no code
0
0
0
Related compounds
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
X mark.svgN  verify  (what is  Yes check.svgYX mark.svgN ?)

Boron nitride is a thermally and chemically resistant refractory compound of boron and nitrogen with the chemical formula BN. It exists in various crystalline forms that are isoelectronic to a similarly structured carbon lattice. The hexagonal form corresponding to graphite is the most stable and soft among BN polymorphs, and is therefore used as a lubricant and an additive to cosmetic products. The cubic (zincblende aka sphalerite structure) variety analogous to diamond is called c-BN; it is softer than diamond, but its thermal and chemical stability is superior. The rare wurtzite BN modification is similar to lonsdaleite but slightly softer than the cubic form. [3]

Contents

Because of excellent thermal and chemical stability, boron nitride ceramics are used in high-temperature equipment and metal casting. Boron nitride has potential use in nanotechnology.

History

Boron nitride was discovered by chemistry teacher of the Liverpool Institute William Henry Balmain  [ de ] in 1842 via reduction of boric acid with charcoal in the presence of potassium cyanide. [4]

Structure

Boron nitride exists in multiple forms that differ in the arrangement of the boron and nitrogen atoms, giving rise to varying bulk properties of the material.

Amorphous form (a-BN)

The amorphous form of boron nitride (a-BN) is non-crystalline, lacking any long-distance regularity in the arrangement of its atoms. It is analogous to amorphous carbon.

All other forms of boron nitride are crystalline.

Hexagonal form (h-BN)

The most stable crystalline form is the hexagonal one, also called h-BN, α-BN, g-BN, and graphitic boron nitride. Hexagonal boron nitride (point group = D3h; space group = P63/mmc) has a layered structure similar to graphite. Within each layer, boron and nitrogen atoms are bound by strong covalent bonds, whereas the layers are held together by weak van der Waals forces. The interlayer "registry" of these sheets differs, however, from the pattern seen for graphite, because the atoms are eclipsed, with boron atoms lying over and above nitrogen atoms. This registry reflects the local polarity of the B–N bonds, as well as interlayer N-donor/B-acceptor characteristics. Likewise, many metastable forms consisting of differently stacked polytypes exist. Therefore, h-BN and graphite are very close neighbors, and the material can accommodate carbon as a substituent element to form BNCs. BC6N hybrids have been synthesized, where carbon substitutes for some B and N atoms. [5] Hexagonal boron nitride monolayer is analogous to graphene, having a honeycomb lattice structure of nearly the same dimensions. Unlike graphene, which is black and an electrical conductor, h-BN monolayer is white and an insulator. It has been proposed for use as an atomic flat insulating substrate or a tunneling dielectric barrier in 2D electronics. . [6]

Cubic form (c-BN)

Cubic boron nitride has a crystal structure analogous to that of diamond. Consistent with diamond being less stable than graphite, the cubic form is less stable than the hexagonal form, but the conversion rate between the two is negligible at room temperature, as it is for diamond. The cubic form has the sphalerite crystal structure (space group = F43m), the same as that of diamond (with ordered B and N atoms), and is also called β-BN or c-BN.

Wurtzite form (w-BN)

The wurtzite form of boron nitride (w-BN; point group = C6v; space group = P63mc) has the same structure as lonsdaleite, a rare hexagonal polymorph of carbon. As in the cubic form, the boron and nitrogen atoms are grouped into tetrahedra. [7] In the wurtzite form, the boron and nitrogen atoms are grouped into 6-membered rings. In the cubic form all rings are in the chair configuration, whereas in w-BN the rings between 'layers' are in boat configuration. Earlier optimistic reports predicted that the wurtzite form was very strong, and was estimated by a simulation as potentially having a strength 18% stronger than that of diamond. Since only small amounts of the mineral exist in nature, this has not yet been experimentally verified. [8] Its hardness is 46 GPa, slightly harder than commercial borides but softer than the cubic form of boron nitride. [3]

Properties

Physical

Properties of amorphous and crystalline BN, graphite and diamond.
Some properties of h-BN and graphite differ within the basal planes (∥) and perpendicular to them (⟂)
MaterialBoron nitride (BN)Graphite [9] Diamond [10]
a- [11] [12] [13] h-c- [14] [10] w-
Density (g/cm3)2.28~2.13.453.49~2.13.515
Knoop hardness (GPa)104534100
Bulk modulus (GPa)10036.540040034440
Thermal conductivity
(W/m·K)
3600 ∥,
30 ⟂
740200–2000 ∥,
2–800 ⟂
600–2000
Thermal expansion (10−6/K)−2.7 ∥, 38 ⟂1.22.7−1.5 ∥, 25 ⟂0.8
Band gap (eV)5.055.9–6.4 [15] 10.1-10.7 [16] 4.5–5.505.5
Refractive index 1.71.82.12.052.4
Magnetic susceptibility
(µemu/g) [17]
−0.48 ∥,
−17.3 ⟂
−0.2 – −2.7 ∥,
−20 – −28 ⟂
−1.6

The partly ionic structure of BN layers in h-BN reduces covalency and electrical conductivity, whereas the interlayer interaction increases resulting in higher hardness of h-BN relative to graphite. The reduced electron-delocalization in hexagonal-BN is also indicated by its absence of color and a large band gap. Very different bonding – strong covalent within the basal planes (planes where boron and nitrogen atoms are covalently bonded) and weak between them – causes high anisotropy of most properties of h-BN.

For example, the hardness, electrical and thermal conductivity are much higher within the planes than perpendicular to them. On the contrary, the properties of c-BN and w-BN are more homogeneous and isotropic.

Those materials are extremely hard, with the hardness of bulk c-BN being slightly smaller and w-BN even higher than that of diamond. [18] Polycrystalline c-BN with grain sizes on the order of 10 nm is also reported to have Vickers hardness comparable or higher than diamond. [19] Because of much better stability to heat and transition metals, c-BN surpasses diamond in mechanical applications, such as machining steel. [20] The thermal conductivity of BN is among the highest of all electric insulators (see table).

Boron nitride can be doped p-type with beryllium and n-type with boron, sulfur, silicon or if co-doped with carbon and nitrogen. [14] Both hexagonal and cubic BN are wide-gap semiconductors with a band-gap energy corresponding to the UV region. If voltage is applied to h-BN [21] [22] or c-BN, [23] then it emits UV light in the range 215–250 nm and therefore can potentially be used as light-emitting diodes (LEDs) or lasers.

Little is known on melting behavior of boron nitride. It degrades at 2973 °C, but melts at elevated pressure. [24] [25]

Thermal stability

Hexagonal and cubic BN (and probably w-BN) show remarkable chemical and thermal stabilities. For example, h-BN is stable to decomposition at temperatures up to 1000 °C in air, 1400 °C in vacuum, and 2800 °C in an inert atmosphere. The reactivity of h-BN and c-BN is relatively similar, and the data for c-BN are summarized in the table below.

Reactivity of c-BN with solids [14]
SolidAmbientActionThreshold temperature (°C)
Mo10−2 Pa vacuumReaction1360
Ni10−2 Pa vacuum Wetting [a] 1360
Fe, Ni, CoArgonReact1400–1500
Al10−2 Pa vacuumWetting and reaction1050
Si10−3 Pa vacuumWetting1500
Cu, Ag, Au, Ga, In, Ge, Sn10−3 Pa vacuumNo wetting1100
BNo wetting2200
Al2O3 + B2O310−2 Pa vacuumNo reaction1360

Thermal stability of c-BN can be summarized as follows: [14]

  • In air or oxygen: B2O3 protective layer prevents further oxidation to ~1300 °C; no conversion to hexagonal form at 1400 °C.
  • In nitrogen: some conversion to h-BN at 1525 °C after 12 h.
  • In vacuum (10−5 Pa): conversion to h-BN at 1550–1600 °C.

Chemical stability

Boron nitride is not attacked by the usual acids, but it is soluble in alkaline molten salts and nitrides, such as LiOH, KOH, NaOH-Na2CO3, NaNO3, Li3N, Mg3N2, Sr3N2, Ba3N2 or Li3BN2, which are therefore used to etch BN. [14]

Thermal conductivity

The theoretical thermal conductivity of hexagonal boron nitride nanoribbons (BNNRs) can approach 1700–2000  W/(mK), which has the same order of magnitude as the experimental measured value for graphene, and can be comparable to the theoretical calculations for graphene nanoribbons. [26] [27] Moreover, the thermal transport in the BNNRs is anisotropic. The thermal conductivity of zigzag-edged BNNRs is about 20% larger than that of armchair-edged nanoribbons at room temperature. [28]

Mechanical properties

BN nanosheets consist of hexagonal boron nitride (h-BN). They are stable up to 800°C in air. The structure of monolayer BN is similar to that of graphene, which has exceptional strength, [29] a high-temperature lubricant, and a substrate in electronic devices. [30]

The anisotropy of Young's modulus and Poisson's ratio depends on the system size. [31] h-BN also exhibits strongly anisotropic strength and toughness, [32] and maintains these over a range of vacancy defects, showing that the anisotropy is independent to the defect type.

Natural occurrence

In 2009, cubic form (c-BN) was reported in Tibet, and the name qingsongite proposed. The substance was found in dispersed micron-sized inclusions in chromium-rich rocks. In 2013, the International Mineralogical Association affirmed the mineral and the name. [33] [34] [35] [36]

Synthesis

Preparation and reactivity of hexagonal BN

Hexagonal boron nitride is obtained by the treating boron trioxide (B2O3) or boric acid (H3BO3) with ammonia (NH3) or urea (CO(NH2)2) in an inert atmosphere: [37]

B2O3 + 2 NH3 → 2 BN + 3 H2O (T = 900 °C)
B(OH)3 + NH3 → BN + 3 H2O (T = 900 °C)
B2O3 + CO(NH2)2 → 2 BN + CO2 + 2 H2O (T > 1000 °C)
B2O3 + 3 CaB6 + 10 N2 → 20 BN + 3 CaO (T > 1500 °C)

The resulting disordered (amorphous) material contains 92–95% BN and 5–8% B2O3. The remaining B2O3 can be evaporated in a second step at temperatures > 1500 °C in order to achieve BN concentration >98%. Such annealing also crystallizes BN, the size of the crystallites increasing with the annealing temperature. [20] [38]

h-BN parts can be fabricated inexpensively by hot-pressing with subsequent machining. The parts are made from boron nitride powders adding boron oxide for better compressibility. Thin films of boron nitride can be obtained by chemical vapor deposition from boron trichloride and nitrogen precursors. [39] ZYP Coatings also has developed boron nitride coatings that may be painted on a surface. Combustion of boron powder in nitrogen plasma at 5500 °C yields ultrafine boron nitride used for lubricants and toners. [40]

Boron nitride reacts with iodine fluoride to give NI3 in low yield. [41] Boron nitride reacts with nitrides of lithium, alkaline earth metals and lanthanides to form nitridoborates. [42] For example:

Li3N + BN → Li3BN2

Intercalation of hexagonal BN

Structure of hexagonal boron nitride intercalated with potassium (
B4N4K) BN8Kstructure.jpg
Structure of hexagonal boron nitride intercalated with potassium (B4N4K)

Various species intercalate into hexagonal BN, such as NH3 intercalate [43] or alkali metals. [44]

Preparation of cubic BN

c-BN is prepared analogously to the preparation of synthetic diamond from graphite. Direct conversion of hexagonal boron nitride to the cubic form has been observed at pressures between 5 and 18 GPa and temperatures between 1730 and 3230 °C, that is similar parameters as for direct graphite-diamond conversion. [45] The addition of a small amount of boron oxide can lower the required pressure to 4–7 GPa and temperature to 1500 °C. As in diamond synthesis, to further reduce the conversion pressures and temperatures, a catalyst is added, such as lithium, potassium, or magnesium, their nitrides, their fluoronitrides, water with ammonium compounds, or hydrazine. [46] [47] Other industrial synthesis methods, again borrowed from diamond growth, use crystal growth in a temperature gradient, or explosive shock wave. The shock wave method is used to produce material called heterodiamond, a superhard compound of boron, carbon, and nitrogen. [48]

Low-pressure deposition of thin films of cubic boron nitride is possible. As in diamond growth, the major problem is to suppress the growth of hexagonal phases (h-BN or graphite, respectively). Whereas in diamond growth this is achieved by adding hydrogen gas, boron trifluoride is used for c-BN. Ion beam deposition, plasma-enhanced chemical vapor deposition, pulsed laser deposition, reactive sputtering, and other physical vapor deposition methods are used as well. [39]

Preparation of wurtzite BN

Wurtzite BN can be obtained via static high-pressure or dynamic shock methods. [49] The limits of its stability are not well defined. Both c-BN and w-BN are formed by compressing h-BN, but formation of w-BN occurs at much lower temperatures close to 1700 °C. [46]

Production statistics

Whereas the production and consumption figures for the raw materials used for BN synthesis, namely boric acid and boron trioxide, are well known (see boron), the corresponding numbers for the boron nitride are not listed in statistical reports. An estimate for the 1999 world production is 300 to 350 metric tons. The major producers and consumers of BN are located in the United States, Japan, China and Germany. In 2000, prices varied from about $75–120/kg for standard industrial-quality h-BN and were about up to $200–400/kg for high purity BN grades. [37]

Applications

Hexagonal BN

Ceramic BN crucible BNcrucible.jpg
Ceramic BN crucible

Hexagonal BN (h-BN) is the most widely used polymorph. It is a good lubricant at both low and high temperatures (up to 900 °C, even in an oxidizing atmosphere). h-BN lubricant is particularly useful when the electrical conductivity or chemical reactivity of graphite (alternative lubricant) would be problematic. In internal combustion engines, where graphite could be oxidized and turn into carbon sludge, h-BN with its superior thermal stability can be added to engine lubricants. As with all nano-particle suspensions, Brownian-motion settlement is a problem. Settlement can clog engine oil filters, which limits solid lubricant applications in a combustion engine to automotive racing, where engine re-building is common. Since carbon has appreciable solubility in certain alloys (such as steels), which may lead to degradation of properties, BN is often superior for high temperature and/or high pressure applications. Another advantage of h-BN over graphite is that its lubricity does not require water or gas molecules trapped between the layers. Therefore, h-BN lubricants can be used in vacuum, such as space applications. The lubricating properties of fine-grained h-BN are used in cosmetics, paints, dental cements, and pencil leads. [50]

Hexagonal BN was first used in cosmetics around 1940 in Japan. Because of its high price, h-BN was abandoned for this application. Its use was revitalized in the late 1990s with the optimization h-BN production processes, and currently h-BN is used by nearly all leading producers of cosmetic products for foundations, make-up, eye shadows, blushers, kohl pencils, lipsticks and other skincare products. [20]

Because of its excellent thermal and chemical stability, boron nitride ceramics and coatings are used high-temperature equipment. h-BN can be included in ceramics, alloys, resins, plastics, rubbers, and other materials, giving them self-lubricating properties. Such materials are suitable for construction of e.g. bearings and in steelmaking. [20] Many quantum devices use multilayer h-BN as a substrate material. It can also be used as a dielectric in resistive random access memories. [51] [52]

Hexagonal BN is used in xerographic process and laser printers as a charge leakage barrier layer of the photo drum. [53] In the automotive industry, h-BN mixed with a binder (boron oxide) is used for sealing oxygen sensors, which provide feedback for adjusting fuel flow. The binder utilizes the unique temperature stability and insulating properties of h-BN. [20]

Parts can be made by hot pressing from four commercial grades of h-BN. Grade HBN contains a boron oxide binder; it is usable up to 550–850 °C in oxidizing atmosphere and up to 1600 °C in vacuum, but due to the boron oxide content is sensitive to water. Grade HBR uses a calcium borate binder and is usable at 1600 °C. Grades HBC and HBT contain no binder and can be used up to 3000 °C. [54]

Boron nitride nanosheets (h-BN) can be deposited by catalytic decomposition of borazine at a temperature ~1100 °C in a chemical vapor deposition setup, over areas up to about 10 cm2. Owing to their hexagonal atomic structure, small lattice mismatch with graphene (~2%), and high uniformity they are used as substrates for graphene-based devices. [55] BN nanosheets are also excellent proton conductors. Their high proton transport rate, combined with the high electrical resistance, may lead to applications in fuel cells and water electrolysis. [56]

h-BN has been used since the mid-2000s as a bullet and bore lubricant in precision target rifle applications as an alternative to molybdenum disulfide coating, commonly referred to as "moly". It is claimed to increase effective barrel life, increase intervals between bore cleaning and decrease the deviation in point of impact between clean bore first shots and subsequent shots. [57]

h-BN is used as a release agent in molten metal and glass applications. For example, ZYP Coatings developed and currently produces a line of paintable h-BN coatings that are used by manufacturers of molten aluminium, non-ferrous metal, and glass. [58] Because h-BN is nonwetting and lubricious to these molten materials, the coated surface (i.e. mold or crucible) does not stick to the material. [59] [60] [61] [62]

Cubic BN

Cubic boron nitride (CBN or c-BN) is widely used as an abrasive. [63] Its usefulness arises from its insolubility in iron, nickel, and related alloys at high temperatures, whereas diamond is soluble in these metals. Polycrystalline c-BN (PCBN) abrasives are therefore used for machining steel, whereas diamond abrasives are preferred for aluminum alloys, ceramics, and stone. When in contact with oxygen at high temperatures, BN forms a passivation layer of boron oxide. Boron nitride binds well with metals due to formation of interlayers of metal borides or nitrides. Materials with cubic boron nitride crystals are often used in the tool bits of cutting tools. For grinding applications, softer binders such as resin, porous ceramics and soft metals are used. Ceramic binders can be used as well. Commercial products are known under names "Borazon" (by Hyperion Materials & Technologies [64] ), and "Elbor" or "Cubonite" (by Russian vendors). [50]

Contrary to diamond, large c-BN pellets can be produced in a simple process (called sintering) of annealing c-BN powders in nitrogen flow at temperatures slightly below the BN decomposition temperature. This ability of c-BN and h-BN powders to fuse allows cheap production of large BN parts. [50]

Similar to diamond, the combination in c-BN of highest thermal conductivity and electrical resistivity is ideal for heat spreaders.

As cubic boron nitride consists of light atoms and is very robust chemically and mechanically, it is one of the popular materials for X-ray membranes: low mass results in small X-ray absorption, and good mechanical properties allow usage of thin membranes, further reducing the absorption. [65]

Amorphous BN

Layers of amorphous boron nitride (a-BN) are used in some semiconductor devices, e.g. MOSFETs. They can be prepared by chemical decomposition of trichloro borazine with caesium, or by thermal chemical vapor deposition methods. Thermal CVD can be also used for deposition of h-BN layers, or at high temperatures, c-BN. [66]

Other forms of boron nitride

Atomically thin boron nitride

Hexagonal boron nitride can be exfoliated to mono or few atomic layer sheets. Due to its analogous structure to that of graphene, atomically thin boron nitride is sometimes called white graphene. [67]

Mechanical properties

Atomically thin boron nitride is one of the strongest electrically insulating materials. Monolayer boron nitride has an average Young's modulus of 0.865TPa and fracture strength of 70.5GPa, and in contrast to graphene, whose strength decreases dramatically with increased thickness, few-layer boron nitride sheets have a strength similar to that of monolayer boron nitride. [68]

Thermal conductivity

Atomically thin boron nitride has one of the highest thermal conductivity coefficients (751 W/mK at room temperature) among semiconductors and electrical insulators, and its thermal conductivity increases with reduced thickness due to less intra-layer coupling. [69]

Thermal stability

The air stability of graphene shows a clear thickness dependence: monolayer graphene is reactive to oxygen at 250 °C, strongly doped at 300 °C, and etched at 450 °C; in contrast, bulk graphite is not oxidized until 800 °C. [70] Atomically thin boron nitride has much better oxidation resistance than graphene. Monolayer boron nitride is not oxidized till 700 °C and can sustain up to 850 °C in air; bilayer and trilayer boron nitride nanosheets have slightly higher oxidation starting temperatures. [71] The excellent thermal stability, high impermeability to gas and liquid, and electrical insulation make atomically thin boron nitride potential coating materials for preventing surface oxidation and corrosion of metals [72] [73] and other two-dimensional (2D) materials, such as black phosphorus. [74]

Better surface adsorption

Atomically thin boron nitride has been found to have better surface adsorption capabilities than bulk hexagonal boron nitride. [75] According to theoretical and experimental studies, atomically thin boron nitride as an adsorbent experiences conformational changes upon surface adsorption of molecules, increasing adsorption energy and efficiency. The synergic effect of the atomic thickness, high flexibility, stronger surface adsorption capability, electrical insulation, impermeability, high thermal and chemical stability of BN nanosheets can increase the Raman sensitivity by up to two orders, and in the meantime attain long-term stability and reusability not readily achievable by other materials. [76] [77]

Dielectric properties

Atomically thin hexagonal boron nitride is an excellent dielectric substrate for graphene, molybdenum disulfide (MoS2), and many other 2D material-based electronic and photonic devices. As shown by electric force microscopy (EFM) studies, the electric field screening in atomically thin boron nitride shows a weak dependence on thickness, which is in line with the smooth decay of electric field inside few-layer boron nitride revealed by the first-principles calculations. [70]

Raman characteristics

Raman spectroscopy has been a useful tool to study a variety of 2D materials, and the Raman signature of high-quality atomically thin boron nitride was first reported by Gorbachev et al. in 2011. [78] and Li et al. [71] However, the two reported Raman results of monolayer boron nitride did not agree with each other. Cai et al., therefore, conducted systematic experimental and theoretical studies to reveal the intrinsic Raman spectrum of atomically thin boron nitride. [79] It reveals that atomically thin boron nitride without interaction with a substrate has a G band frequency similar to that of bulk hexagonal boron nitride, but strain induced by the substrate can cause Raman shifts. Nevertheless, the Raman intensity of G band of atomically thin boron nitride can be used to estimate layer thickness and sample quality.

BN nanomesh observed with a scanning tunneling microscope. The center of each ring corresponds to the center of the pores STMnm-2.JPG
BN nanomesh observed with a scanning tunneling microscope. The center of each ring corresponds to the center of the pores
Top: absorption of cyclohexane by BN aerogel. Cyclohexane is stained with Sudan II red dye and is floating on water. Bottom: reuse of the aerogel after burning in air. Oil absorption by BN aerogel.jpg
Top: absorption of cyclohexane by BN aerogel. Cyclohexane is stained with Sudan II red dye and is floating on water. Bottom: reuse of the aerogel after burning in air.

Boron nitride nanomesh

Boron nitride nanomesh is a nanostructured two-dimensional material. It consists of a single BN layer, which forms by self-assembly a highly regular mesh after high-temperature exposure of a clean rhodium [81] or ruthenium [82] surface to borazine under ultra-high vacuum. The nanomesh looks like an assembly of hexagonal pores. The distance between two pore centers is 3.2 nm and the pore diameter is ~2 nm. Other terms for this material are boronitrene or white graphene. [83]

The boron nitride nanomesh is air-stable [84] and compatible with some liquids. [85] [86] up to temperatures of 800 °C. [81]

BN nanotubes are flame resistant, as shown in this comparative test of airplanes made of cellullose, carbon buckypaper and BN nanotube buckypaper. Flame test of buckypapers.jpg
BN nanotubes are flame resistant, as shown in this comparative test of airplanes made of cellullose, carbon buckypaper and BN nanotube buckypaper.

Boron nitride nanotubes

Boron nitride tubules were first made in 1989 by Shore and Dolan This work was patented in 1989 and published in 1989 thesis (Dolan) and then 1993 Science. The 1989 work was also the first preparation of amorphous BN by B-trichloroborazine and cesium metal.

Boron nitride nanotubes were predicted in 1994 [88] and experimentally discovered in 1995. [89] They can be imagined as a rolled up sheet of h-boron nitride. Structurally, it is a close analog of the carbon nanotube, namely a long cylinder with diameter of several to hundred nanometers and length of many micrometers, except carbon atoms are alternately substituted by nitrogen and boron atoms. However, the properties of BN nanotubes are very different: whereas carbon nanotubes can be metallic or semiconducting depending on the rolling direction and radius, a BN nanotube is an electrical insulator with a bandgap of ~5.5 eV, basically independent of tube chirality and morphology. [90] In addition, a layered BN structure is much more thermally and chemically stable than a graphitic carbon structure. [91] [92]

Boron nitride aerogel

Boron nitride aerogel is an aerogel made of highly porous BN. It typically consists of a mixture of deformed BN nanotubes and nanosheets. It can have a density as low as 0.6 mg/cm3 and a specific surface area as high as 1050 m2/g, and therefore has potential applications as an absorbent, catalyst support and gas storage medium. BN aerogels are highly hydrophobic and can absorb up to 160 times their weight in oil. They are resistant to oxidation in air at temperatures up to 1200 °C, and hence can be reused after the absorbed oil is burned out by flame. BN aerogels can be prepared by template-assisted chemical vapor deposition using borazine as the feed gas. [80]

Composites containing BN

Addition of boron nitride to silicon nitride ceramics improves the thermal shock resistance of the resulting material. For the same purpose, BN is added also to silicon nitride-alumina and titanium nitride-alumina ceramics. Other materials being reinforced with BN include alumina and zirconia, borosilicate glasses, glass ceramics, enamels, and composite ceramics with titanium boride-boron nitride, titanium boride-aluminium nitride-boron nitride, and silicon carbide-boron nitride composition. [93]

Zirconia Stabilized Boron Nitride (ZSBN) is produced by adding zirconia to BN, enhancing its thermal shock resistance and mechanical strength through a sintering process. [94] It offers better performance characteristics including Superior corrosion and erosion resistance over a wide temperature range. [95] Its unique combination of thermal conductivity, lubricity, mechanical strength, and stability makes it suitable for various applications including cutting tools and wear-resistant coatings, thermal and electrical insulation, aerospace and defense, and high-temperature components. [96] [97]

Pyrolytic boron nitride (PBN)

Pyrolytic boron nitride (PBN), also known as Chemical vapour-deposited Boron Nitride(CVD-BN), [98] is a high-purity ceramic material characterized by exceptional chemical resistance and mechanical strength at high temperatures. [99] Pyrolytic boron nitride is typically prepared through the thermal decomposition of boron trichloride and ammonia vapors on graphite substrates at 1900°C. [100]

Pyrolytic boron nitride (PBN) generally has a hexagonal structure similar to hexagonal boron nitride (hBN), though it can exhibit stacking faults or deviations from the ideal lattice. [101] Pyrolytic boron nitride (PBN) shows some remarkable attributes, including exceptional chemical inertness, high dielectric strength, excellent thermal shock resistance, non-wettability, non-toxicity, oxidation resistance, and minimal outgassing. [102] [103]

Due to a highly ordered planar texture similar to pyrolytic graphite (PG), it exhibits anisotropic properties such as lower dielectric constant vertical to the crystal plane and higher bending strength along the crystal plane. [104] PBN material has been widely manufactured as crucibles of compound semiconductor crystals, output windows and dielectric rods of traveling-wave tubes, high-temperature jigs and insulator. [105]

Health issues

Boron nitride (along with Si3N4, NbN, and BNC) is generally considered to be non-toxic and does not exhibit chemical activity in biological systems. [106] Due to its excellent safety profile and lubricious properties, boron nitride finds widespread use in various applications, including cosmetics and food processing equipment. [107] [108]

See also

Notes

  1. Here wetting refers to the ability of a molten metal to keep contact with solid BN

Related Research Articles

<span class="mw-page-title-main">Boron</span> Chemical element with atomic number 5 (B)

Boron is a chemical element. It has the symbol B and atomic number 5. In its crystalline form it is a brittle, dark, lustrous metalloid; in its amorphous form it is a brown powder. As the lightest element of the boron group it has three valence electrons for forming covalent bonds, resulting in many compounds such as boric acid, the mineral sodium borate, and the ultra-hard crystals of boron carbide and boron nitride.

<span class="mw-page-title-main">Chemical vapor deposition</span> Method used to apply surface coatings

Chemical vapor deposition (CVD) is a vacuum deposition method used to produce high-quality, and high-performance, solid materials. The process is often used in the semiconductor industry to produce thin films.

<span class="mw-page-title-main">Molybdenum disulfide</span> Chemical compound

Molybdenum disulfide is an inorganic compound composed of molybdenum and sulfur. Its chemical formula is MoS2.

<span class="mw-page-title-main">Allotropes of carbon</span> Materials made only out of carbon

Carbon is capable of forming many allotropes due to its valency (tetravalent). Well-known forms of carbon include diamond and graphite. In recent decades, many more allotropes have been discovered and researched, including ball shapes such as buckminsterfullerene and sheets such as graphene. Larger-scale structures of carbon include nanotubes, nanobuds and nanoribbons. Other unusual forms of carbon exist at very high temperatures or extreme pressures. Around 500 hypothetical 3‑periodic allotropes of carbon are known at the present time, according to the Samara Carbon Allotrope Database (SACADA).

<span class="mw-page-title-main">Graphene</span> Hexagonal lattice made of carbon atoms

Graphene is a carbon allotrope consisting of a single layer of atoms arranged in a honeycomb planar nanostructure. The name "graphene" is derived from "graphite" and the suffix -ene, indicating the presence of double bonds within the carbon structure.

<span class="mw-page-title-main">Superhard material</span> Material with Vickers hardness exceeding 40 gigapascals

A superhard material is a material with a hardness value exceeding 40 gigapascals (GPa) when measured by the Vickers hardness test. They are virtually incompressible solids with high electron density and high bond covalency. As a result of their unique properties, these materials are of great interest in many industrial areas including, but not limited to, abrasives, polishing and cutting tools, disc brakes, and wear-resistant and protective coatings.

<span class="mw-page-title-main">Boron compounds</span>

Boron compounds are compounds containing the element boron. In the most familiar compounds, boron has the formal oxidation state +3. These include oxides, sulfides, nitrides, and halides.

<span class="mw-page-title-main">Nanomesh</span> Inorganic nanostructured two-dimensional material

The nanomesh is an inorganic nanostructured two-dimensional material, similar to graphene. It was discovered in 2003 at the University of Zurich, Switzerland.

<span class="mw-page-title-main">Alex Zettl</span> American nano-scale physicist

Alex K. Zettl is an American experimental physicist, educator, and inventor.

<span class="mw-page-title-main">Graphitic carbon nitride</span> Class of chemical compounds

Graphitic carbon nitride (g-C3N4) is a family of carbon nitride compounds with a general formula near to C3N4 (albeit typically with non-zero amounts of hydrogen) and two major substructures based on heptazine and poly(triazine imide) units which, depending on reaction conditions, exhibit different degrees of condensation, properties and reactivities.

<span class="mw-page-title-main">Borophene</span> Allotrope of boron

Borophene is a crystalline atomic monolayer of boron, i.e., it is a two-dimensional allotrope of boron and also known as boron sheet. First predicted by theory in the mid-1990s, different borophene structures were experimentally confirmed in 2015.

<span class="mw-page-title-main">Transition metal dichalcogenide monolayers</span> Thin semiconductors

Transition-metal dichalcogenide (TMD or TMDC) monolayers are atomically thin semiconductors of the type MX2, with M a transition-metal atom (Mo, W, etc.) and X a chalcogen atom (S, Se, or Te). One layer of M atoms is sandwiched between two layers of X atoms. They are part of the large family of so-called 2D materials, named so to emphasize their extraordinary thinness. For example, a MoS2 monolayer is only 6.5 Å thick. The key feature of these materials is the interaction of large atoms in the 2D structure as compared with first-row transition-metal dichalcogenides, e.g., WTe2 exhibits anomalous giant magnetoresistance and superconductivity.

In materials science, the term single-layer materials or 2D materials refers to crystalline solids consisting of a single layer of atoms. These materials are promising for some applications but remain the focus of research. Single-layer materials derived from single elements generally carry the -ene suffix in their names, e.g. graphene. Single-layer materials that are compounds of two or more elements have -ane or -ide suffixes. 2D materials can generally be categorized as either 2D allotropes of various elements or as compounds.

A two-dimensional semiconductor is a type of natural semiconductor with thicknesses on the atomic scale. Geim and Novoselov et al. initiated the field in 2004 when they reported a new semiconducting material graphene, a flat monolayer of carbon atoms arranged in a 2D honeycomb lattice. A 2D monolayer semiconductor is significant because it exhibits stronger piezoelectric coupling than traditionally employed bulk forms. This coupling could enable applications. One research focus is on designing nanoelectronic components by the use of graphene as electrical conductor, hexagonal boron nitride as electrical insulator, and a transition metal dichalcogenide as semiconductor.

A rapidly increasing list of graphene production techniques have been developed to enable graphene's use in commercial applications.

<span class="mw-page-title-main">Boron nitride nanotube</span> Polymorph of boron nitride

Boron nitride nanotubes (BNNTs) are a polymorph of boron nitride. They were predicted in 1994 and experimentally discovered in 1995. Structurally they are similar to carbon nanotubes, which are cylinders with sub-micrometer diameters and micrometer lengths, except that carbon atoms are alternately substituted by nitrogen and boron atoms. However, the properties of BN nanotubes are very different: whereas carbon nanotubes can be metallic or semiconducting depending on the rolling direction and radius, a BN nanotube is an electrical insulator with a bandgap of ~5.5 eV, basically independent of tube chirality and morphology. In addition, a layered BN structure is much more thermally and chemically stable than a graphitic carbon structure. BNNTs have unique physical and chemical properties, when compared to Carbon Nanotubes (CNTs) providing a very wide range of commercial and scientific applications. Although BNNTs and CNTs share similar tensile strength properties of circa 100 times stronger than steel and 50 times stronger than industrial-grade carbon fibre, BNNTs can withstand high temperatures of up to 900 °C. as opposed to CNTs which remain stable up to temperatures of 400 °C, and are also capable of absorbing radiation. BNNTS are packed with physicochemical features including high hydrophobicity and considerable hydrogen storage capacity and they are being investigated for possible medical and biomedical applications, including gene delivery, drug delivery, neutron capture therapy, and more generally as biomaterials BNNTs are also superior to CNTs in the way they bond to polymers giving rise to many new applications and composite materials.

Graphene-Boron Nitride nanohybrid materials are a class of compounds created from graphene and boron nitride nanosheets. Graphene and boron nitride both contain intrinsic thermally conductive and electrically insulative properties. The combination of these two compounds may be useful to advance the development and understanding of electronics.

<span class="mw-page-title-main">Boron nitride nanosheet</span>

Boron nitride nanosheet is a crystalline form of the hexagonal boron nitride (h-BN), which has a thickness of one atom. Similar in geometry as well as physical and thermal properties to its carbon analog graphene, but has very different chemical and electronic properties – contrary to the black and highly conducting graphene, BN nanosheets are electrical insulators with a band gap of ~5.9 eV, and therefore appear white in color.

A graphene morphology is any of the structures related to, and formed from, single sheets of graphene. 'Graphene' is typically used to refer to the crystalline monolayer of the naturally occurring material graphite. Due to quantum confinement of electrons within the material at these low dimensions, small differences in graphene morphology can greatly impact the physical and chemical properties of these materials. Commonly studied graphene morphologies include the monolayer sheets, bilayer sheets, graphene nanoribbons and other 3D structures formed from stacking of the monolayer sheets.

Two dimensional hexagonal boron nitride is a material of comparable structure to graphene with potential applications in e.g. photonics., fuel cells and as a substrate for two-dimensional heterostructures. 2D h-BN is isostructural to graphene, but where graphene is conductive, 2D h-BN is a wide-gap insulator.

References

  1. 1 2 3 4 for h-BN
  2. 1 2 3 4 Haynes, William M., ed. (2011). CRC Handbook of Chemistry and Physics (92nd ed.). Boca Raton, FL: CRC Press. p. 5.6. ISBN   1-4398-5511-0.
  3. 1 2 Brazhkin, Vadim V.; Solozhenko, Vladimir L. (2019). "Myths about new ultrahard phases: Why materials that are significantly superior to diamond in elastic moduli and hardness are impossible". Journal of Applied Physics. 125 (13): 130901. arXiv: 1811.09503 . Bibcode:2019JAP...125m0901B. doi:10.1063/1.5082739. S2CID   85517548.
  4. Balmain, W. H. (October 1842). "Observations on the formation of compounds of boron and silicon with nitrogen and certain metals". The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science. 21 (138): 270–277. doi:10.1080/14786444208621545. ISSN   1941-5966.
  5. Kawaguchi, M.; et al. (2008). "Electronic Structure and Intercalation Chemistry of Graphite-Like Layered Material with a Composition of BC6N". Journal of Physics and Chemistry of Solids. 69 (5–6): 1171. Bibcode:2008JPCS...69.1171K. doi:10.1016/j.jpcs.2007.10.076.
  6. Ba K, Jiang W, Cheng J, Bao J, et al. (2017). "Chemical and Bandgap Engineering in Monolayer Hexagonal Boron Nitride". Scientific Reports. 7 (1): 45584. Bibcode:2017NatSR...745584B. doi: 10.1038/srep45584 . PMC   5377335 . PMID   28367992. S2CID   22951232.
  7. Silberberg, M. S. (2009). Chemistry: The Molecular Nature of Matter and Change (5th ed.). New York: McGraw-Hill. p. 483. ISBN   978-0-07-304859-8.
  8. Griggs, Jessica (2014-05-13). "Diamond no longer nature's hardest material". New Scientist. Retrieved 2018-01-12.
  9. Delhaes, P. (2001). Graphite and Precursors. CRC Press. ISBN   978-9056992286.
  10. 1 2 "BN – Boron Nitride". Ioffe Institute Database.
  11. Zedlitz, R. (1996). "Properties of Amorphous Boron Nitride Thin Films". Journal of Non-Crystalline Solids. 198–200 (Part 1): 403. Bibcode:1996JNCS..198..403Z. doi:10.1016/0022-3093(95)00748-2.
  12. Henager, C. H. Jr. (1993). "Thermal Conductivities of Thin, Sputtered Optical Films". Applied Optics. 32 (1): 91–101. Bibcode:1993ApOpt..32...91H. doi:10.1364/AO.32.000091. PMID   20802666.
  13. Weissmantel, S. (1999). "Microstructure and Mechanical Properties of Pulsed Laser Deposited Boron Nitride Films". Diamond and Related Materials. 8 (2–5): 377. Bibcode:1999DRM.....8..377W. doi:10.1016/S0925-9635(98)00394-X.
  14. 1 2 3 4 5 Leichtfried, G.; et al. (2002). "13.5 Properties of diamond and cubic boron nitride". In P. Beiss; et al. (eds.). Landolt-Börnstein – Group VIII Advanced Materials and Technologies: Powder Metallurgy Data. Refractory, Hard and Intermetallic Materials. Landolt-Börnstein - Group VIII Advanced Materials and Technologies. Vol. 2A2. Berlin: Springer. pp. 118–139. doi:10.1007/b83029. ISBN   978-3-540-42961-6.
  15. Su, C. (2022). "Tuning colour centres at a twisted hexagonal boron nitride interface". Nature Materials. 21 (8): 896–902. Bibcode:2022NatMa..21..896S. doi:10.1038/s41563-022-01303-4. OSTI   1906698. PMID   35835818. S2CID   250535073.
  16. Tararan, Anna; di Sabatino, Stefano; Gatti, Matteo; Taniguchi, Takashi; Watanabe, Kenji; Reining, Lucia; Tizei, Luiz H. G.; Kociak, Mathieu; Zobelli, Alberto (2018). "Optical gap and optically active intragap defects in cubic BN". Phys. Rev. B. 98 (9): 094106. arXiv: 1806.11446 . Bibcode:2018PhRvB..98i4106T. doi:10.1103/PhysRevB.98.094106. S2CID   119097213.
  17. Crane, T. P.; Cowan, B. P. (2000). "Magnetic Relaxation Properties of Helium-3 Adsorbed on Hexagonal Boron Nitride". Physical Review B. 62 (17): 11359. Bibcode:2000PhRvB..6211359C. doi:10.1103/PhysRevB.62.11359.
  18. Pan, Z.; et al. (2009). "Harder than Diamond: Superior Indentation Strength of Wurtzite BN and Lonsdaleite". Physical Review Letters. 102 (5): 055503. Bibcode:2009PhRvL.102e5503P. doi:10.1103/PhysRevLett.102.055503. PMID   19257519.
  19. Tian, Yongjun; et al. (2013). "Ultrahard nanotwinned cubic boron nitride". Nature. 493 (7432): 385–8. Bibcode:2013Natur.493..385T. doi:10.1038/nature11728. PMID   23325219. S2CID   4419843.
  20. 1 2 3 4 5 Engler, M. (2007). "Hexagonal Boron Nitride (hBN) – Applications from Metallurgy to Cosmetics" (PDF). Cfi/Ber. DKG. 84: D25. ISSN   0173-9913.
  21. Kubota, Y.; et al. (2007). "Deep Ultraviolet Light-Emitting Hexagonal Boron Nitride Synthesized at Atmospheric Pressure". Science. 317 (5840): 932–4. Bibcode:2007Sci...317..932K. doi: 10.1126/science.1144216 . PMID   17702939.
  22. Watanabe, K.; Taniguchi, T.; Kanda, H. (2004). "Direct-Bandgap Properties and Evidence for Ultraviolet Lasing of Hexagonal Boron Nitride Single Crystal". Nature Materials. 3 (6): 404–9. Bibcode:2004NatMa...3..404W. doi:10.1038/nmat1134. PMID   15156198. S2CID   23563849.
  23. Taniguchi, T.; et al. (2002). "Ultraviolet Light Emission from Self-Organized p–n Domains in Cubic Boron Nitride Bulk Single Crystals Grown Under High Pressure". Applied Physics Letters. 81 (22): 4145. Bibcode:2002ApPhL..81.4145T. doi:10.1063/1.1524295.
  24. Dreger, Lloyd H.; et al. (1962). "Sublimation and Decomposition Studies on Boron Nitride and Aluminum Nitride". The Journal of Physical Chemistry. 66 (8): 1556. doi:10.1021/j100814a515.
  25. Wentorf, R. H. (1957). "Cubic Form of Boron Nitride". The Journal of Chemical Physics. 26 (4): 956. Bibcode:1957JChPh..26..956W. doi:10.1063/1.1745964.
  26. Lan, J. H.; et al. (2009). "Thermal Transport in Hexagonal Boron Nitride Nanoribbons". Physical Review B. 79 (11): 115401. Bibcode:2009PhRvB..79k5401L. doi:10.1103/PhysRevB.79.115401.
  27. Hu J, Ruan X, Chen YP (2009). "Thermal Conductivity and Thermal Rectification in Graphene Nanoribbons: A Molecular Dynamics Study". Nano Letters. 9 (7): 2730–5. arXiv: 1008.1300 . Bibcode:2009NanoL...9.2730H. doi:10.1021/nl901231s. PMID   19499898. S2CID   1157650.
  28. Ouyang, Tao; Chen, Yuanping; Xie, Yuee; Yang, Kaike; Bao, Zhigang; Zhong, Jianxin (2010). "Thermal Transport in Hexagonal Boron Nitride Nanoribbons". Nanotechnology. 21 (24): 245701. Bibcode:2010Nanot..21x5701O. doi:10.1088/0957-4484/21/24/245701. PMID   20484794. S2CID   12898097.
  29. Falin, Aleksey; Cai, Qiran; Santos, Elton J. G.; Scullion, Declan; Qian, Dong; Zhang, Rui; Yang, Zhi; Huang, Shaoming; Watanabe, Kenji; Taniguchi, Takashi; Barnett, Matthew R.; Chen, Ying; Ruoff, Rodney S.; Li, Lu Hua (2017-06-22). "Mechanical properties of atomically thin boron nitride and the role of interlayer interactions". Nature Communications. 8 (1): 15815. arXiv: 2008.01657 . Bibcode:2017NatCo...815815F. doi:10.1038/ncomms15815. ISSN   2041-1723. PMC   5489686 . PMID   28639613.
  30. Bosak, Alexey; Serrano, Jorge; Krisch, Michael; Watanabe, Kenji; Taniguchi, Takashi; Kanda, Hisao (2006-01-19). "Elasticity of hexagonal boron nitride: Inelastic x-ray scattering measurements". Physical Review B. 73 (4): 041402. Bibcode:2006PhRvB..73d1402B. doi:10.1103/PhysRevB.73.041402. ISSN   1098-0121.
  31. Thomas, Siby; Ajith, K M; Valsakumar, M C (2016-07-27). "Directional anisotropy, finite size effect and elastic properties of hexagonal boron nitride". Journal of Physics: Condensed Matter. 28 (29): 295302. Bibcode:2016JPCM...28C5302T. doi:10.1088/0953-8984/28/29/295302. ISSN   0953-8984. PMID   27255345.
  32. Ahmed, Tousif; Procak, Allison; Hao, Tengyuan; Hossain, Zubaer M. (2019-04-17). "Strong anisotropy in strength and toughness in defective hexagonal boron nitride". Physical Review B. 99 (13): 134105. Bibcode:2019PhRvB..99m4105A. doi:10.1103/PhysRevB.99.134105. ISSN   2469-9950.
  33. Dobrzhinetskaya, L.F.; et al. (2013). "Qingsongite, IMA 2013-030". CNMNC Newsletter. 16: 2708.
  34. Dobrzhinetskaya, L.F.; et al. (2014). "Qingsongite, natural cubic boron nitride: The first boron mineral from the Earth's mantle" (PDF). American Mineralogist. 99 (4): 764–772. Bibcode:2014AmMin..99..764D. doi:10.2138/am.2014.4714. S2CID   130947756. Archived (PDF) from the original on 2022-10-09.
  35. "Qingsongite".
  36. "List of Minerals". 21 March 2011.
  37. 1 2 Rudolph, S. (2000). "Boron Nitride (BN)". American Ceramic Society Bulletin. 79: 50. Archived from the original on 2012-03-06.
  38. "Synthesis of Boron Nitride from Oxide Precursors". Archived from the original on December 12, 2007. Retrieved 2009-06-06.
  39. 1 2 Mirkarimi, P. B.; et al. (1997). "Review of Advances in Cubic Boron Nitride Film Synthesis". Materials Science and Engineering: R: Reports. 21 (2): 47–100. doi:10.1016/S0927-796X(97)00009-0.
  40. Paine, Robert T.; Narula, Chaitanya K. (1990). "Synthetic Routes to Boron Nitride". Chemical Reviews. 90: 73–91. doi:10.1021/cr00099a004.
  41. Tornieporth-Oetting, I.; Klapötke, T. (1990). "Nitrogen Triiodide". Angewandte Chemie International Edition. 29 (6): 677–679. doi:10.1002/anie.199006771.
  42. Housecroft, Catherine E.; Sharpe, Alan G. (2005). Inorganic Chemistry (2d ed.). Pearson education. p. 318. ISBN   978-0-13-039913-7.
  43. Solozhenko, V. L.; et al. (2002). "In situ Studies of Boron Nitride Crystallization from BN Solutions in Supercritical N–H Fluid at High Pressures and Temperatures". Physical Chemistry Chemical Physics. 4 (21): 5386. Bibcode:2002PCCP....4.5386S. doi:10.1039/b206005a.
  44. Doll, G. L.; et al. (1989). "Intercalation of Hexagonal Boron Nitride with Potassium". Journal of Applied Physics. 66 (6): 2554. Bibcode:1989JAP....66.2554D. doi:10.1063/1.344219.
  45. Wentorf, R. H. Jr. (March 1961). "Synthesis of the Cubic Form of Boron Nitride". Journal of Chemical Physics. 34 (3): 809–812. Bibcode:1961JChPh..34..809W. doi:10.1063/1.1731679.
  46. 1 2 Vel, L.; et al. (1991). "Cubic Boron Nitride: Synthesis, Physicochemical Properties and Applications". Materials Science and Engineering: B. 10 (2): 149. doi:10.1016/0921-5107(91)90121-B.
  47. Fukunaga, O. (2002). "Science and Technology in the Recent Development of Boron Nitride Materials". Journal of Physics: Condensed Matter. 14 (44): 10979. Bibcode:2002JPCM...1410979F. doi:10.1088/0953-8984/14/44/413. S2CID   250835481.
  48. Komatsu, T.; et al. (1999). "Creation of Superhard B–C–N Heterodiamond Using an Advanced Shock Wave Compression Technology". Journal of Materials Processing Technology. 85 (1–3): 69. doi:10.1016/S0924-0136(98)00263-5.
  49. Soma, T.; et al. (1974). "Characterization of Wurtzite Type Boron Nitride Synthesized by Shock Compression". Materials Research Bulletin. 9 (6): 755. doi:10.1016/0025-5408(74)90110-X.
  50. 1 2 3 Greim, Jochen; Schwetz, Karl A. (2005). "Boron Carbide, Boron Nitride, and Metal Borides". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a04_295.pub2. ISBN   978-3527306732.
  51. Pan, Chengbin; Ji, Yanfeng; Xiao, Na; Hui, Fei; Tang, Kechao; Guo, Yuzheng; Xie, Xiaoming; Puglisi, Francesco M.; Larcher, Luca (2017-01-01). "Coexistence of Grain-Boundaries-Assisted Bipolar and Threshold Resistive Switching in Multilayer Hexagonal Boron Nitride". Advanced Functional Materials. 27 (10): 1604811. doi:10.1002/adfm.201604811. hdl: 11380/1129421 . S2CID   100500198.
  52. Puglisi, F. M.; Larcher, L.; Pan, C.; Xiao, N.; Shi, Y.; Hui, F.; Lanza, M. (2016-12-01). "2D h-BN based RRAM devices". 2016 IEEE International Electron Devices Meeting (IEDM). pp. 34.8.1–34.8.4. doi:10.1109/IEDM.2016.7838544. ISBN   978-1-5090-3902-9. S2CID   28059875.
  53. Schein, L. B. (1988). "Electrophotography and Development Physics". Physics Today. Springer Series in Electrophysics. 14 (12). Berlin: Springer-Verlag: 66–68. Bibcode:1989PhT....42l..66S. doi:10.1063/1.2811250. ISBN   9780387189024.
  54. Harper, Charles A. (2001). Handbook of Ceramics, Glasses and Diamonds. McGraw-Hill. ISBN   978-0070267121.
  55. Park, Ji-Hoon; Park, Jin Cheol; Yun, Seok Joon; Kim, Hyun; Luong, Dinh Hoa; Kim, Soo Min; Choi, Soo Ho; Yang, Woochul; Kong, Jing; Kim, Ki Kang; Lee, Young Hee (2014). "Large-Area Monolayer Hexagonal Boron Nitride on Pt Foil". ACS Nano. 8 (8): 8520–8. doi:10.1021/nn503140y. PMID   25094030.
  56. Hu, S.; et al. (2014). "Proton transport through one-atom-thick crystals". Nature. 516 (7530): 227–230. arXiv: 1410.8724 . Bibcode:2014Natur.516..227H. doi:10.1038/nature14015. PMID   25470058. S2CID   4455321.
  57. "Hexagonal Boron Nitride (HBN)—How Well Does It Work?". AccurateShooter.com. 8 September 2014. Retrieved 28 December 2015.
  58. "colourdeverre.com/img/projects/advancedpriming.pdf" (PDF).
  59. "Wettability, Spreading, and Interfacial Phenomena in High-Temperature Coatings".
  60. "Substrate Release Mechanisms for Gas Metal Arc 3-D Aluminum Metal Printing. 3D Printing &Additive Manufacturing".
  61. "Wear properties of squeeze cast in situ Mg2Si–A380 alloy".
  62. "INTERFACIAL REACTION WETTING IN THE BORON NITRIDE/MOLTEN ALUMINUM SYSTEM" (PDF).
  63. Todd RH, Allen DK, Dell KAlting L (1994). Manufacturing Processes Reference Guide. Industrial Press Inc. pp. 43–48. ISBN   978-0-8311-3049-7.
  64. "Diamond and Cubic Boron Nitride (CBN) Abrasives". Hyperion Materials & Technologies. Retrieved 21 June 2022.
  65. El Khakani, M. A.; Chaker, M. (1993). "Physical Properties of the X-Ray Membrane Materials". Journal of Vacuum Science and Technology B. 11 (6): 2930–2937. Bibcode:1993JVSTB..11.2930E. doi:10.1116/1.586563.
  66. Schmolla, W. (1985). "Positive Drift Effect of BN-InP Enhancement N-Channel MISFET". International Journal of Electronics. 58: 35. doi:10.1080/00207218508939000.
  67. Li, Lu Hua; Chen, Ying (2016). "Atomically Thin Boron Nitride: Unique Properties and Applications". Advanced Functional Materials. 26 (16): 2594–2608. arXiv: 1605.01136 . Bibcode:2016arXiv160501136L. doi:10.1002/adfm.201504606. S2CID   102038593.
  68. Falin, Aleksey; Cai, Qiran; Santos, Elton J.G.; Scullion, Declan; Qian, Dong; Zhang, Rui; Yang, Zhi; Huang, Shaoming; Watanabe, Kenji (2017-06-22). "Mechanical properties of atomically thin boron nitride and the role of interlayer interactions". Nature Communications. 8: 15815. arXiv: 2008.01657 . Bibcode:2017NatCo...815815F. doi:10.1038/ncomms15815. PMC   5489686 . PMID   28639613.
  69. Cai, Qiran; Scullion, Declan; Gan, Wei; Falin, Alexey; Zhang, Shunying; Watanabe, Kenji; Taniguchi, Takashi; Chen, Ying; Santos, Elton J. G. (2019). "High thermal conductivity of high-quality monolayer boron nitride and its thermal expansion". Science Advances. 5 (6): eaav0129. arXiv: 1903.08862 . Bibcode:2019SciA....5..129C. doi:10.1126/sciadv.aav0129. ISSN   2375-2548. PMC   6555632 . PMID   31187056.
  70. 1 2 Li, Lu Hua; Santos, Elton J. G.; Xing, Tan; Cappelluti, Emmanuele; Roldán, Rafael; Chen, Ying; Watanabe, Kenji; Taniguchi, Takashi (2015). "Dielectric Screening in Atomically Thin Boron Nitride Nanosheets". Nano Letters. 15 (1): 218–223. arXiv: 1503.00380 . Bibcode:2015NanoL..15..218L. doi:10.1021/nl503411a. PMID   25457561. S2CID   207677623.
  71. 1 2 Li, Lu Hua; Cervenka, Jiri; Watanabe, Kenji; Taniguchi, Takashi; Chen, Ying (2014). "Strong Oxidation Resistance of Atomically Thin Boron Nitride Nanosheets". ACS Nano. 8 (2): 1457–1462. arXiv: 1403.1002 . Bibcode:2014arXiv1403.1002L. doi:10.1021/nn500059s. PMID   24400990. S2CID   5372545.
  72. Li, Lu Hua; Xing, Tan; Chen, Ying; Jones, Rob (2014). "Nanosheets: Boron Nitride Nanosheets for Metal Protection (Adv. Mater. Interfaces 8/2014)". Advanced Materials Interfaces. 1 (8): n/a. doi: 10.1002/admi.201470047 .
  73. Liu, Zheng; Gong, Yongji; Zhou, Wu; Ma, Lulu; Yu, Jingjiang; Idrobo, Juan Carlos; Jung, Jeil; MacDonald, Allan H.; Vajtai, Robert (2013-10-04). "Ultrathin high-temperature oxidation-resistant coatings of hexagonal boron nitride". Nature Communications. 4 (1): 2541. Bibcode:2013NatCo...4.2541L. doi: 10.1038/ncomms3541 . PMID   24092019.
  74. Chen, Xiaolong; Wu, Yingying; Wu, Zefei; Han, Yu; Xu, Shuigang; Wang, Lin; Ye, Weiguang; Han, Tianyi; He, Yuheng (2015-06-23). "High-quality sandwiched black phosphorus heterostructure and its quantum oscillations". Nature Communications. 6 (1): 7315. arXiv: 1412.1357 . Bibcode:2015NatCo...6.7315C. doi:10.1038/ncomms8315. PMC   4557360 . PMID   26099721.
  75. Cai, Qiran; Du, Aijun; Gao, Guoping; Mateti, Srikanth; Cowie, Bruce C. C.; Qian, Dong; Zhang, Shuang; Lu, Yuerui; Fu, Lan (2016-08-29). "Molecule-Induced Conformational Change in Boron Nitride Nanosheets with Enhanced Surface Adsorption". Advanced Functional Materials. 26 (45): 8202–8210. arXiv: 1612.02883 . Bibcode:2016arXiv161202883C. doi:10.1002/adfm.201603160. S2CID   13800939.
  76. Cai, Qiran; Mateti, Srikanth; Yang, Wenrong; Jones, Rob; Watanabe, Kenji; Taniguchi, Takashi; Huang, Shaoming; Chen, Ying; Li, Lu Hua (2016-05-20). "Inside Back Cover: Boron Nitride Nanosheets Improve Sensitivity and Reusability of Surface-Enhanced Raman Spectroscopy (Angew. Chem. Int. Ed. 29/2016)". Angewandte Chemie International Edition. 55 (29): 8457. doi: 10.1002/anie.201604295 . hdl: 10536/DRO/DU:30086239 .
  77. Cai, Qiran; Mateti, Srikanth; Watanabe, Kenji; Taniguchi, Takashi; Huang, Shaoming; Chen, Ying; Li, Lu Hua (2016-06-14). "Boron Nitride Nanosheet-Veiled Gold Nanoparticles for Surface-Enhanced Raman Scattering". ACS Applied Materials & Interfaces. 8 (24): 15630–15636. arXiv: 1606.07183 . Bibcode:2016arXiv160607183C. doi:10.1021/acsami.6b04320. PMID   27254250. S2CID   206424168.
  78. Gorbachev, Roman V.; Riaz, Ibtsam; Nair, Rahul R.; Jalil, Rashid; Britnell, Liam; Belle, Branson D.; Hill, Ernie W.; Novoselov, Kostya S.; Watanabe, Kenji (2011-01-07). "Hunting for Monolayer Boron Nitride: Optical and Raman Signatures". Small. 7 (4): 465–468. arXiv: 1008.2868 . doi:10.1002/smll.201001628. PMID   21360804. S2CID   17344540.
  79. Cai, Qiran; Scullion, Declan; Falin, Aleksey; Watanabe, Kenji; Taniguchi, Takashi; Chen, Ying; Santos, Elton J. G.; Li, Lu Hua (2017). "Raman signature and phonon dispersion of atomically thin boron nitride". Nanoscale. 9 (9): 3059–3067. arXiv: 2008.01656 . doi:10.1039/c6nr09312d. PMID   28191567. S2CID   206046676.
  80. 1 2 Song, Yangxi; Li, Bin; Yang, Siwei; Ding, Guqiao; Zhang, Changrui; Xie, Xiaoming (2015). "Ultralight boron nitride aerogels via template-assisted chemical vapor deposition". Scientific Reports. 5: 10337. Bibcode:2015NatSR...510337S. doi:10.1038/srep10337. PMC   4432566 . PMID   25976019.
  81. 1 2 Corso, M.; et al. (2004). "Boron Nitride Nanomesh". Science. 303 (5655): 217–220. Bibcode:2004Sci...303..217C. doi:10.1126/science.1091979. PMID   14716010. S2CID   11964344.
  82. Goriachko, A.; et al. (2007). "Self-Assembly of a Hexagonal Boron Nitride Nanomesh on Ru(0001)". Langmuir. 23 (6): 2928–2931. doi:10.1021/la062990t. PMID   17286422.
  83. Graphene and Boronitrene (White Graphene) Archived 2018-05-28 at the Wayback Machine . physik.uni-saarland.de
  84. Bunk, O.; et al. (2007). "Surface X-Ray Diffraction Study of Boron-Nitride Nanomesh in Air". Surface Science. 601 (2): L7–L10. Bibcode:2007SurSc.601L...7B. doi:10.1016/j.susc.2006.11.018.
  85. Berner, S.; et al. (2007). "Boron Nitride Nanomesh: Functionality from a Corrugated Monolayer". Angewandte Chemie International Edition. 46 (27): 5115–5119. doi:10.1002/anie.200700234. PMID   17538919.
  86. Widmer, R.; et al. (2007). "Electrolytic in situ STM Investigation of h-BN-Nanomesh" (PDF). Electrochemical Communications. 9 (10): 2484–2488. doi:10.1016/j.elecom.2007.07.019. Archived (PDF) from the original on 2022-10-09.
  87. Kim, Keun Su; Jakubinek, Michael B.; Martinez-Rubi, Yadienka; Ashrafi, Behnam; Guan, Jingwen; O'Neill, K.; Plunkett, Mark; Hrdina, Amy; Lin, Shuqiong; Dénommée, Stéphane; Kingston, Christopher; Simard, Benoit (2015). "Polymer nanocomposites from free-standing, macroscopic boron nitride nanotube assemblies". RSC Adv. 5 (51): 41186. Bibcode:2015RSCAd...541186K. doi:10.1039/C5RA02988K.
  88. Rubio, A.; et al. (1994). "Theory of Graphitic Boron Nitride Nanotubes". Physical Review B. 49 (7): 5081–5084. Bibcode:1994PhRvB..49.5081R. doi:10.1103/PhysRevB.49.5081. PMID   10011453.
  89. Chopra, N. G.; et al. (1995). "Boron Nitride Nanotubes". Science. 269 (5226): 966–7. Bibcode:1995Sci...269..966C. doi:10.1126/science.269.5226.966. PMID   17807732. S2CID   28988094.
  90. Blase, X.; et al. (1994). "Stability and Band Gap Constancy of Boron Nitride Nanotubes". Europhysics Letters (EPL). 28 (5): 335. Bibcode:1994EL.....28..335B. doi:10.1209/0295-5075/28/5/007. S2CID   120010610.
  91. Han, Wei-Qiang; et al. (2002). "Transformation of BxCyNz Nanotubes to Pure BN Nanotubes" (PDF). Applied Physics Letters. 81 (6): 1110. Bibcode:2002ApPhL..81.1110H. doi:10.1063/1.1498494.
  92. Golberg, D.; Bando, Y.; Tang, C. C.; Zhi, C. Y. (2007). "Boron Nitride Nanotubes". Advanced Materials. 19 (18): 2413. Bibcode:2007AdM....19.2413G. doi:10.1002/adma.200700179. S2CID   221149452.
  93. Lee, S. M. (1992). Handbook of Composite Reinforcements. John Wiley and Sons. ISBN   978-0471188612.
  94. Lisa, Ross. "Diverse Classification Factors of Boron Nitride and Their Correlation with PBN, HBN, CBN, and ZSBN Variants". Precise Ceramics. Retrieved June 8, 2024.
  95. New Steel: Mini & Integrated Mill Management and Technologies. Chilton Publishing. 1996. pp. 51–56.
  96. Hayat, Asif; Sohail, Muhammad; Hamdy, Mohamed (2022). "Fabrication, characteristics, and applications of boron nitride and their composite nanomaterials". Surfaces and Interfaces. 29. doi:10.1016/j.surfin.2022.101725 . Retrieved June 8, 2024.
  97. Eichler, Jens; Lesniak, Cristoph (2008). "Boron nitride (BN) and BN composites for high-temperature applications". Journal of the European Ceramic Society. 28 (5): 1105–1109. doi:10.1016/j.jeurceramsoc.2007.09.005.
  98. Rose, Lisa. "About Pyrolytic Boron Nitride". Precise Ceramic. Retrieved May 31, 2024.
  99. "Pyrolytic Boron Nitride (PBN)". Shin-Etsu Chemical Co., Ltd. Retrieved May 31, 2024.
  100. Moore, A. (1969-03-22). "Compression Annealing of Pyrolytic Boron Nitride". Nature. 221 (5186): 1133–1135. Bibcode:1969Natur.221.1133M. doi:10.1038/2211133a0 . Retrieved May 31, 2024.
  101. "An Overview of Pyrolytic Boron Nitride (PBN)". Sputter Targets. 3 December 2018. Retrieved May 31, 2024.
  102. Lipp, A.; Schwetz, K.A.; Hunold, K. (1989). "Hexagonal boron nitride: Fabrication, properties and applications". Journal of the European Ceramic Society. 5 (1): 3–9. doi:10.1016/0955-2219(89)90003-4.
  103. Moore, A.W. (1990). "Characterization of pyrolytic boron nitride for semiconductor materials processing". Journal of Crystal Growth. 106 (1): 6–15. Bibcode:1990JCrGr.106....6M. doi:10.1016/0022-0248(90)90281-O.
  104. Rebillat, F.; Guette, A. (1997). "Highly ordered pyrolytic BN obtained by LPCVD". Journal of the European Ceramic Society. 17 (12): 1403–1414. doi:10.1016/S0955-2219(96)00244-0.
  105. Gao, Shitao; Li, Bin (2018). "Micromorphology and structure of pyrolytic boron nitride synthesized by chemical vapor deposition from borazine". Ceramics International. 44 (10): 11424–11430. doi:10.1016/j.ceramint.2018.03.201.
  106. "EWG Skin Deep® | What is BORON NITRIDE". EWG. Retrieved 2023-07-26.
  107. "UNII - 2U4T60A6YD". precision.fda.gov. Retrieved 2023-07-26.
  108. "NSF International / Nonfood Compounds Registration Program" (PDF).