sp.SUP.2.-sp.SUP.3 .Hybrid crystalline boron nitride and its preparation process

Abstract

The present disclosure relates to a novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride and its preparation process. A novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride allotrope, named Gradia BN, is synthesized using sp.sup.2 or sp.sup.3 hybridized boron nitride as raw materials under high-temperature and high-pressure. The basic structural units of Gradia BN are composed of sp.sup.2 hybridized graphite-like structural units and sp.sup.3 hybridized diamond-like structural units. Gradia BN disclosed in the present disclosure is a class of new sp.sup.2-sp.sup.3 hybrid boron nitride allotrope, whose crystal structure can vary with the widths and/or crystallographic orientation relationships of internal sp.sup.2 and/or sp.sup.3 structural units, and may have variable physical properties.

Claims

1. An sp.sup.2-sp.sup.3 hybrid crystalline boron nitride, wherein its basic structural unit is composed of sp.sup.2 hybridized graphite-like structural unit and sp.sup.3 hybridized diamond-like structural unit, and wherein the sp2 hybridized graphite-like structural unit and the sp3 hybridized diamond-like structural unit are connected via a coherent interface.

2. The sp.sup.2-sp.sup.3 hybrid crystalline boron nitride according to claim 1, being a monocrystal with a space group of 4 (P2.sub.1) or 6 (Pm) or 8 (Cm) or a polycrystal composed of two or more different phases, each of which phases having a space group of 4 (P2.sub.1) or 6 (Pm) or 8 (Cm).

3. A process for the preparation of the sp.sup.2-sp.sup.3 hybrid crystalline boron nitride as defined in claim 1, comprising the steps of: (1) loading the boron nitride raw material into a pre-pressing mold, pre-forming the boron nitride raw material into a body by using a press, and then placing it in a vacuum hot-pressing sintering furnace for pre-sintering; (2) putting the pre-sintered boron nitride raw material body as obtained in step (1) into an assembly block, and then drying the assembly block containing the pre-sintered boron nitride raw material body; (3) placing the assembly block as obtained in step (2) in a press and subjecting it to high-temperature and high-pressure treatment; and (4) taking out the assembly block from the press to obtain the sp.sup.2-sp.sup.3 hybrid crystalline boron nitride after a pressure relief and cooling.

4. The process for the preparation of the sp.sup.2-sp.sup.3 hybrid crystalline boron nitride according to claim 3, wherein step (1) further comprises purifying the boron nitride raw material by an acid solution to remove impurities, cleaning it using methanol and then drying it before it is loaded into the pre-pressing mold.

5. The process for the preparation of the sp.sup.2-sp.sup.3 hybrid crystalline boron nitride according to claim 4, wherein the high-temperature and high-pressure treatment of step (3) is carried out at a pressure of 3-25 GPa and a temperature of 600-2500° C. for a period of 5-120 minutes.

6. The process for the preparation of the sp.sup.2-sp.sup.3 hybrid crystalline boron nitride according to claim 5, wherein the boron nitride raw material is one or more sp.sup.2 hybridized boron nitride materials selected from the group consisting of hexagonal boron nitride (hBN), rhombohedral boron nitride (rBN), disordered boron nitride (pBN and tBN), graphene-like boron nitride (BN monolayer or nanomesh), boron nitride nanotubes (BN nanotubes), onion boron nitride (oBN) and amorphous boron nitride (aBN), one or more sp.sup.3 hybridized boron nitride materials selected from the group consisting of sphalerite boron nitride (cBN) and wurtzite boron nitride (wBN), or a mixture of sp.sup.2 hybridized boron nitride materials and sp.sup.3 hybridized boron nitride materials.

7. The process for the preparation of the sp.sup.2-sp.sup.3 hybrid crystalline boron nitride according to claim 4, wherein the boron nitride raw material is one or more sp.sup.2 hybridized boron nitride materials selected from the group consisting of hexagonal boron nitride (hBN), rhombohedral boron nitride (rBN), disordered boron nitride (pBN and tBN), graphene-like boron nitride (BN monolayer or nanomesh), boron nitride nanotubes (BN nanotubes), onion boron nitride (oBN) and amorphous boron nitride (aBN), one or more sp.sup.3 hybridized boron nitride materials selected from the group consisting of sphalerite boron nitride (cBN) and wurtzite boron nitride (wBN), or a mixture of sp.sup.2 hybridized boron nitride materials and sp.sup.3 hybridized boron nitride materials.

8. The process for the preparation of the sp.sup.2-sp.sup.3 hybrid crystalline boron nitride according to claim 3, wherein the pre-sintering step of step (1) is carried out at a temperature of 200-1800° C. for a period of 5-60 minutes.

9. The process for the preparation of the sp.sup.2-sp.sup.3 hybrid crystalline boron nitride according to claim 3, wherein the drying step of step (2) is carried out at a temperature of 100-200° C. for 1-3 h.

10. The process for the preparation of the sp.sup.2-sp.sup.3 hybrid crystalline boron nitride according to claim 3, wherein the high-temperature and high-pressure treatment is carried out at a pressure of 3-25 GPa and a temperature of 600-2500° C. for a period of 5-120 minutes.

11. The process for the preparation of the sp.sup.2-sp.sup.3 hybrid crystalline boron nitride according to claim 10, wherein the boron nitride raw material is one or more sp.sup.2 hybridized boron nitride materials selected from the group consisting of hexagonal boron nitride (hBN), rhombohedral boron nitride (rBN), disordered boron nitride (pBN and tBN), graphene-like boron nitride (BN monolayer or nanomesh), boron nitride nanotubes (BN nanotubes), onion boron nitride (oBN) and amorphous boron nitride (aBN), one or more sp.sup.3 hybridized boron nitride materials selected from the group consisting of sphalerite boron nitride (cBN) and wurtzite boron nitride (wBN), or a mixture of sp.sup.2 hybridized boron nitride materials and sp.sup.3 hybridized boron nitride materials.

12. The process for the preparation of the sp.sup.2-sp.sup.3 hybrid crystalline boron nitride according to claim 3, wherein the boron nitride raw material is one or more sp.sup.2 hybridized boron nitride materials selected from the group consisting of hexagonal boron nitride (hBN), rhombohedral boron nitride (rBN), disordered boron nitride (pBN and tBN), graphene-like boron nitride (BN monolayer or nanomesh), boron nitride nanotubes (BN nanotubes), onion boron nitride (oBN) and amorphous boron nitride (aBN), one or more sp.sup.3 hybridized boron nitride materials selected from the group consisting of sphalerite boron nitride (cBN) and wurtzite boron nitride (wBN), or a mixture of sp.sup.2 hybridized boron nitride materials and sp.sup.3 hybridized boron nitride materials.

Description

DRAWINGS

(1) FIG. 1 shows the high-resolution TEM images of four typical types of Gradia BN, wherein the dark spheres represent N atoms and the light spheres represent B atoms.

(2) FIG. 2 shows the crystal structure of Gradia-I BN containing 12 BN formula units per unit cell, according to the present disclosure.

(3) FIG. 3 shows the crystal structure of Gradia-II containing 24 BN formula units per unit cell, according to the present disclosure.

(4) FIG. 4 shows the crystal structure of Gradia-III containing 48 BN formula units per unit cell, according to the present disclosure.

(5) FIG. 5 shows the crystal structure of Gradia-IV containing 24 BN formula units per unit cell, according to the present disclosure.

(6) FIG. 6 shows an electron energy loss spectrum (EELS) and a selected area electron diffraction (SAED) pattern of Gradia BN, a novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride allotrope prepared in accordance with Example 1 of the present disclosure, as measured by Themis Z transmission electron microscope.

(7) FIG. 7 shows the Vickers hardness data and photograph of a Gradia BN sample prepared in accordance with Example 7 of the present disclosure as well as a photograph of indentation obtained from the Vickers hardness test under 5 Kg load.

DETAILED DESCRIPTION

(8) The present inventions will be further described in detail below with reference to the drawings and specific embodiments.

(9) The present disclosure provides an sp.sup.2-sp.sup.3 hybrid crystalline boron nitride (named Gradia BN), wherein its basic structural unit is composed of sp.sup.2 hybridized graphite-like structural unit and sp.sup.3 hybridized diamond-like structural unit, and the two types of units are connected via a coherent interface.

(10) In the context of the present disclosure, the term “basic structural unit” should be understood to refer to the basic structure or main constituent unit of a material, which accounts for at least 70% (e.g. 75%), preferably at least 80% (e.g. 85%), and more preferably at least 90% (e.g. 95% or 99%) of the total weight of the material.

(11) Gradia BN as disclosed herein is a novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride allotrope having a structure completely different from other known crystalline boron nitrides. The basic structure of Gradia BN are composed of sp.sup.2 hybridized graphite-like structural units and sp.sup.3 hybridized diamond-like structural units. Its crystal structure may vary with the widths and/or crystallographic orientation relationships of the internal sp.sup.2 and/or sp.sup.3 structural units. In particular, the sp.sup.3 hybridized diamond-like structural units may be cubic-diamond-like structural units or hexagonal-diamond-like structural units. In addition, according to the needs of specific application scenarios, the molar ratio of the sp.sup.2 hybridized graphite-like structural units to the sp.sup.3 hybridized diamond-like structural units may vary within a broad range, e.g. from 1:9 to 9:1, from 2:8 to 8:2, from 3:7 to 7:3, from 4:6 to 6:4 or about 5:5, and can be adjusted by controlling/adjusting the synthesis parameters for the material, e.g. the temperature and pressure.

(12) The present disclosure further provides a process for the preparation of Gradia BN, comprising subjecting a boron nitride material to high-temperature and high-pressure treatment.

(13) Some preferred embodiments of the process for the preparation of Gradia BN comprises the steps of:

(14) (1) Loading a boron nitride raw material into a pre-pressing mold, pre-forming the boron nitride raw material into a body by using a press, and then placing it in a vacuum hot-pressing sintering furnace for pre-sintering;

(15) (2) Putting the pre-sintered boron nitride raw material body as obtained in step (1) into an assembly block, and then drying the assembly block containing the boron nitride raw material body (e.g. by putting the assembly block containing the boron nitride raw material body into a drying box);

(16) (3) Placing the assembly block as obtained in step (2) in a press for high-temperature and high-pressure treatment, optionally after it is cooled;

(17) (4) Taking out the assembly block from the press to obtain the sp.sup.2-sp.sup.3 hybrid crystalline boron nitride after a pressure relief and cooling.

(18) In preferred embodiments, the boron nitride raw material may be sp.sup.2 hybridized boron nitride materials or sp.sup.3 hybridized boron nitride materials. The sp.sup.2 hybridized boron nitride materials may comprise any one or several of sp.sup.2 hybridized boron nitride materials, such as hexagonal boron nitride (hBN) with graphite like structure, rhombohedral boron nitride (rBN), disordered boron nitride (pBN and tBN), graphene-like boron nitride (BN monolayer or nanomesh), boron nitride nanotubes (BN nanotubes), onion boron nitride (oBN), amorphous boron nitride (aBN) and other boron nitride materials containing sp.sup.2 hybridization. The sp.sup.3 hybridized boron nitride materials may comprise any one or several of sp.sup.3 hybridized boron nitride materials such as sphalerite boron nitride (cBN) and wurtzite boron nitride (wBN). The boron nitride raw materials may also be a mixture of sp.sup.2 hybridized boron nitride materials and sp.sup.3 hybridized boron nitride materials.

(19) In addition, it is desirable to wash the raw materials with a dilute acid solution to remove the impurities present therein, such as silicon (Si), oxygen (O), iron (Fe), aluminum (Al), hydrogen (H), and the like, as to achieve Gradia BN products with superior properties. The washed materials need to be cleaned and dried before being loaded into the pre-pressing mold.

(20) In preferred embodiments, the pre-sintering step of step (1) is carried out at a temperature of 200-1800° C. for a period of 5-60 minutes.

(21) In preferred embodiments, the pre-formed body of step (1) is a cylinder.

(22) In preferred embodiments, the drying step of step (2) is carried out at a temperature of 100-200° C. for 1-3 h.

(23) In preferred embodiments, the high-temperature and high-pressure treatment of step (3) is carried out at a pressure of 3-25 GPa (e.g. from 4 GPa, 5 GPa, 6 GPa, 7 GPa, 8 GPa, 9 GPa, 10 GPa, 11 GPa or 12 GPa to 16 GPa, 17 GPa, 18 GPa, 19 GPa, 20 GPa, 21 GPa, 22 GPa, 23 GPa or 24 GPa) and a temperature of 600-2500° C. (e.g. from 650° C., 700° C., 750° C., 800° C., 850° C. or 900° C. to 1000° C., 1200° C., 1400° C., 1600° C., 1800° C., 2000° C., 2200° C. or 2400° C.). The high-temperature and high-pressure treatment of step (3) is usually to pressurize first, then heat up, and then keep the pressure and temperature for a period of holding time. The holding time is not critical and may be determined according to the selected pressure and temperature. The holding time is preferably about 5-120 minutes, e.g. 10-100 minutes or 20-60 minutes. The high-temperature and high-pressure treatment of step (3) may be carried out in an apparatus e.g. (but not limited to) T25 type press supplied by Rockland Research (USA).

(24) In preferred embodiments, the novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride material synthesized by the above preparation process has a crystal structure variable with the changes of the internal sp.sup.2-hybridized graphite-like structural unit and sp.sup.3-hybridized diamond-like structural unit. In particular, the crystal structure of the novel sp.sup.2-sp.sup.3 hybrid boron nitride can vary with the widths and/or crystallographic orientation relationships of the internal sp.sup.2 and sp.sup.3 structural units, which can be controlled by e.g. changing the raw materials used and adjusting the synthesis pressure and temperature used in the preparation process.

(25) In a particularly preferred embodiment, the present disclosure discloses a process for preparing Gradia BN, comprising the following steps:

(26) (1) loading one or more boron nitride raw materials, including e.g. sp.sup.2 hybridized boron nitride materials such as hBN, rBN, BN nanotubes, aBN or oBN, into a pre-pressing mold, pre-forming the raw boron nitride materials into a cylinder raw material body by using a press, and then placing it in a vacuum hot-pressing sintering furnace for pre-sintering, wherein the pre-sintering is carried out at a temperature of 200-1800° C. and a pressure of 20-50 MPa for a period of 5-60 min;

(27) (2) Putting the pre-sintered boron nitride raw material body as obtained in step (1) into an assembly block, and then putting the assembly block containing the boron nitride raw material body into a drying box for drying wherein the drying is carried out at a temperature of 100-200° C. for 1-3 h;

(28) (3) Taking out the assembly block of step (2) and cooling it to room temperature, and then placing it in a T25 type press supplied by Rockland Research (USA) for high-temperature and high-pressure treatment, wherein the high-temperature and high-pressure treatment is carried out at a pressure of 3-25 GPa and a temperature of 600-2500° C. for a holding time of 5-120 min;

(29) (4) After the press is cooled and depressurized, taking out the assembly block from the press and disassembling the assembly block around the sintered body sample to obtain a novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride, i.e. Gradia BN.

(30) The inventors have prepared a lot of Gradia BN samples by adjusting the synthesis parameters involved in the preparation process. Further investigations show that the Gradia boron nitride samples as obtained can be a single crystal or a polycrystalline form, and their crystal structures may have four kinds of basic configurations. The sp.sup.2-sp.sup.3 hybrid Gradia BN samples have been observed by Themis Z transmission electron microscope, and the typical results are shown in FIG. 1 and FIG. 6. As shown in the EELS spectra in FIG. 6, Gradia BN has both sp.sup.2 hybridization and sp.sup.3 hybridization. It can be seen from the high-resolution images in FIG. 1 that the new sp.sup.2-sp.sup.3 hybrid Gradia boron nitride prepared according to the present disclosure has both sp.sup.2 hybridized graphite-like structure unit and sp.sup.3 hybridized diamond-like structure unit, and may have four kinds of basic configurations depending on the different interface matching relationship. In each configuration, the size of the internal sp.sup.2 hybridized graphite-like structure unit and the size of the internal sp.sup.3 hybridized diamond-like structure unit may change. As shown in FIG. 2 to FIG. 5, there are four monoclinic crystal structures found in the samples prepared according to the present disclosure, which are respectively named as Gradia-I BN, Gradia-II BN, Gradia-III BN and Gradia-IV BN.

(31) The space group of Gradia-I BN is 6 (Pm) or 8 (Cm) depending on the sizes of its internal sp.sup.2 and sp.sup.3 structural units. The Gradia-I BN with space group of 6 (Pm) is shown in FIG. 2. Taking a crystal structure with 12 BN formula units per unit cell as an example, its lattice constants are a=3.6216 Å, b=2.5161 Å, c=18.5246 Å, R=91.7313°. As seen from FIG. 2, Gradia-I BN is a novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride formed by graphite-like structural unit (left part) and cubic-diamond-like structural unit (right part) connected with a specific coherent interface. Gradia BN with this type of coherent interface as shown in FIG. 2 belongs to Gradia-I BN with space group of 6 (Pm) or 8 (Cm).

(32) The space group of Gradia-II BN is 8 (Cm). As shown in FIG. 3, taking a crystal structure with 24 BN formula units per unit cell as an example, its lattice constants are a=13.0068 Å, b=2.5152 Å, c=20.5419 Å, β=95.966°. As seen from FIG. 3, Gradia-II BN is a novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride formed by graphite-like structural unit (left part) and cubic-diamond-like structural unit (right part) connected with a specific coherent interface. Gradia BN with this type of coherent interface as shown in FIG. 3 belongs to Gradia-II BN with space group of 8 (Cm).

(33) The space group of Gradia-III BN is 4 (P2.sub.1). As shown in FIG. 4, taking a crystal structure with 48 BN formula units per unit cell as an example, its lattice constants are a=6.735799 Å, b=4.23985 Å, c=24.038511 Å, β=93.6611°. As seen from FIG. 4, Gradia-III BN is a novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride formed by graphite-like structural unit (left part) and hexagonal-diamond-like structural unit (right part) connected with a specific coherent interface. Gradia BN with this type of coherent interface as shown in FIG. 4 belongs to Gradia-III BN with space group of 4 (P2.sub.1).

(34) The space group of Gradia-IV BN is 6 (Pm). As shown in FIG. 5, taking a crystal structure with 24 BN formula units per unit cell as an example, its lattice constants are a=6.0502 Å, b=2.5089 Å, c=21.1643 Å, β=91.8807°. As seen from FIG. 5, Gradia-IV BN is a novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride formed by graphite-like structural unit (left part) and hexagonal-diamond-like structural unit (right part) connected with a specific coherent interface. Gradia BN with this type of coherent interface as shown in FIG. 5 belongs to Gradia-IV BN with space group of 6 (Pm).

(35) Therefore, Gradia BN as disclosed in the present disclosure may be a monocrystal with a space group of 4 (P2.sub.1) or 6 (Pm) or 8 (Cm) or a polycrystal composed of two or more different phases, each of which phases having a space group of 4 (P2.sub.1) or 6 (Pm) or 8 (Cm).

EXAMPLES

(36) The raw materials used in the examples were all commercially available sp.sup.2 or sp.sup.3 hybridized boron nitride materials, including sp.sup.2 hybridized boron nitride materials such as hBN, rBN, pBN, tBN, BN monolayer or nanomesh, BN nanotubes, oBN, and aBN, and sp.sup.3 hybridized boron nitride materials such as cBN and wBN.

(37) For the high-temperature and high-pressure treatments in the examples, a T25 type press supplied by Rockland Research (USA) was used, and the synthesis pressure and temperature ranges were 3-25 GPa and 25-2500° C., respectively. However, it should be noted that high-temperature and high-pressure equipment involved in the present disclosure is not limited to the T25 type press, and other high-pressure equipment capable of achieving the corresponding pressure and temperature conditions are likewise suitable for the preparation of Gradia BN.

Example 1: Preparation of Gradia BN Using hBN as Boron Nitride Raw Material

(38) (1) The raw material hBN was filled into a pre-pressing mold, and the pre-pressing process was carried out at a pressure of 40 MPa for about 5 minutes using a press to obtain a cylinder body. Then, it was placed into a vacuum hot-pressing sintering furnace for pre-sintering, wherein the pre-sintering temperature was set at 1500° C. and the pre-sintering time was about 40 min.

(39) (2) The pre-sintered boron nitride raw material body as obtained in step (1) was put into an assembly block, and then the assembly block containing the boron nitride raw material body was put into a drying box for drying wherein the drying temperature was 180° C. and the drying time was 2 h.

(40) (3) The assembly block as obtained in step (2) was taken out from the drying box and allowed to cool, and then was placed into a T25 type press supplied by Rockland Research (USA) for high-temperature and high-pressure treatment, wherein the synthesis pressure was 15 GPa, the synthesis temperature was 900° C. and the holding time was 120 min. Then, the press was cooled and depressurized.

(41) (4) The assembly block was taken out from the press, thereby a novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride, i.e. Gradia BN, was obtained.

(42) The obtained product was observed and analyzed through Themis Z transmission electron microscope and the results are shown in FIG. 6. The selected area electron diffraction (SAED) result demonstrates that the synthesized Gradia BN is a boron nitride material having a novel structure; and the electron energy loss spectrum (EELS) result demonstrates that it is an sp.sup.2-sp.sup.3 hybrid boron nitride (see FIG. 6). The high resolution transmission electron microscopy image demonstrates that its structural unit is composed of graphite-like structural unit and diamond-like structural unit (see FIG. 1). The crystallographic analysis shows that the sample as obtained contains Gradia-III BN and Gradia-IV BN.

Example 2: Preparation of Gradia BN Using Sp.SUP.2 .Hybridized Boron Nitride Nanotubes as Boron Nitride Raw Material

(43) (1) BN nanotubes were filled into a pre-pressing mold, and the pre-pressing process was carried out at a pressure of 30 MPa for about 10 minutes using a press to obtain a cylinder body. Then, it was placed into a vacuum hot-pressing sintering furnace for pre-sintering, wherein the pre-sintering temperature was set at 1400° C. and the pre-sintering time was about 15-20 min.

(44) (2) The pre-sintered boron nitride nanotubes body as obtained in step (1) was put into an assembly block, and then the assembly block containing the boron nitride nanotubes body was put into a drying box for drying wherein the drying temperature was 180° C. and the drying time was 2 h.

(45) (3) The assembly block as obtained in step (2) was taken out from the drying box and allowed to cool, and then was placed into a T25 type press supplied by Rockland Research (USA) for high-temperature and high-pressure treatment, wherein the synthesis pressure was 20 GPa, the synthesis temperature was 1200° C. and the holding time was 30 min. Then, the press was cooled and depressurized.

(46) (4) The assembly block was taken out from the press, thereby a novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride, i.e. Gradia BN, was obtained.

(47) The obtained product was observed and analyzed through Themis Z transmission electron microscope. The SAED and EELS results are similar to those shown in FIG. 6. The SAED result demonstrates that the synthesized Gradia BN is a boron nitride material having a novel structure; and the EELS result demonstrates that it is an sp.sup.2-sp.sup.3 hybrid boron nitride. The high resolution transmission electron microscopy image demonstrates that its structural unit is composed of graphite-like structural unit and diamond-like structural unit (see FIG. 1). The crystallographic analysis shows that the sample as obtained contains Gradia-I BN and Gradia-II BN.

Example 3: Preparation of Gradia BN Using Onion BN (oBN) as Boron Nitride Raw Material

(48) (1) The raw material oBN was filled into a pre-pressing mold, and the pre-pressing process was carried out at a pressure of 50 MPa for about 15 minutes using a press to obtain a cylinder body.

(49) (2) The boron nitride raw material body as obtained in step (1) was put into an assembly block, and then the assembly block containing the boron nitride raw material body was put into a drying box for drying wherein the drying temperature was 180° C. and the drying time was 2 h.

(50) (3) The assembly block as obtained in step (2) was taken out from the drying box and allowed to cool, and then was placed into a T25 type press supplied by Rockland Research (USA) for high-temperature and high-pressure treatment, wherein the synthesis pressure was 18 GPa, the synthesis temperature was 1800° C. and the holding time was 60 min. Then, the press was cooled and depressurized.

(51) (4) The assembly block was taken out from the press, thereby a novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride, i.e. Gradia BN, was obtained.

(52) The obtained product was observed and analyzed through Themis Z transmission electron microscope. The SAED and EELS results are similar to those shown in FIG. 6. The SAED result demonstrates that the synthesized Gradia BN is a boron nitride material having a novel structure; and the EELS result demonstrates that it is an sp.sup.2-sp.sup.3 hybrid boron nitride. The high resolution transmission electron microscopy image demonstrates that its structural unit is composed of graphite-like structural unit and diamond-like structural unit (see FIG. 1). The crystallographic analysis shows that the sample as obtained contains Gradia-I BN, Gradia-II BN, Gradia III-BN, and Gradia-IV BN.

Example 4: Preparation of Gradia BN Using Onion BN (oBN) as Boron Nitride Raw Material

(53) The steps (1) to (4) of Example 3 were repeated except that in step (3) the synthesis pressure was 20 GPa and the synthesis temperature was 800° C.

(54) The obtained product was observed and analyzed through Themis Z transmission electron microscope. The SAED and EELS results are similar to those shown in FIG. 6. The SAED result demonstrates that the synthesized Gradia BN is a boron nitride material having a novel structure; and the EELS result demonstrates that it is an sp.sup.2-sp.sup.3 hybrid boron nitride. The high resolution transmission electron microscopy image demonstrates that its structural unit is composed of graphite-like structural unit and diamond-like structural unit (see FIG. 1). The crystallographic analysis shows that the sample as obtained contains Gradia-I BN (with a space group of 6 (Pm) or 8 (Cm)), Gradia-II BN (with a space group of 8 (Cm)), Gradia III-BN (with a space group of 4 (P2.sub.1)) and Gradia-IV BN (with a space group of 6 (Pm)).

Example 5: Preparation of Gradia BN Using hBN as Boron Nitride Raw Material

(55) (1) The raw material hBN was put into dilute hydrochloric acid solution to remove impurities. Then, after hBN was separated from the acid solution, it was rinsed by methanol for several times. The rinsed hBN was then dried, affording the purified hBN raw material. Then, the purified hBN was filled into a pre-pressing mold, and the pre-pressing process was carried out at a pressure of 20 MPa for about 5 minutes using a press to obtain a cylinder body. Then, it was placed into a vacuum hot-pressing sintering furnace for pre-sintering, wherein the pre-sintering temperature was set at 1200° C., the pre-sintering pressure was set at 30 MPa and the pre-sintering time was about 20 min.

(56) (2) The pre-sintered boron nitride raw material body as obtained in step (1) was put into an assembly block, and then the assembly block containing the boron nitride raw material body was put into a drying box for drying wherein the drying temperature was 180° C. and the drying time was 2 h.

(57) (3) The assembly block as obtained in step (2) was taken out from the drying box and allowed to cool, and then was placed into a T25 type press supplied by Rockland Research (USA) for high-temperature and high-pressure treatment, wherein the synthesis pressure was 15 GPa, the synthesis temperature was 1000° C. and the holding time was 60 min. Then, the press was cooled and depressurized.

(58) (4) The assembly block was taken out from the press, thereby a novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride, i.e. Gradia BN, was obtained.

(59) The obtained product was observed and analyzed through Themis Z transmission electron microscope. The SAED and EELS results are similar to those shown in FIG. 6. The SAED result demonstrates that the synthesized Gradia BN is a boron nitride material having a novel structure; and the EELS result demonstrates that it is an sp.sup.2-sp.sup.3 hybrid boron nitride. The high resolution transmission electron microscopy image demonstrates that its structural unit is composed of graphite-like structural unit and diamond-like structural unit (see FIG. 1). The crystallographic analysis shows that the sample as obtained contains Gradia-I BN (with a space group of 6 (Pm) or 8 (Cm)) and Gradia-II BN (with a space group of 8 (Cm)).

Example 6: Preparation of Gradia BN Using cBN as Boron Nitride Raw Material

(60) (1) The raw material cBN powders were pretreated by purification and vacuum heating to remove the impurities such as adsorbed oxygen, adsorbed water and bound water. In particular, the purification was carried out by acid dissolution. Then, the purified cBN powders were filled into the mold of a vacuum hot pressing furnace for further treatment, wherein the vacuum degree was below 5×10.sup.−2, the temperature was 1600° C., the pressure was 30 MPa and the holding time was 15 min.

(61) (2) The pre-sintered boron nitride raw material body as obtained in step (1) was put into an assembly block, and then the assembly block containing the boron nitride raw material body was put into a drying box for drying wherein the drying temperature was 180° C. and the drying time was 2 h.

(62) (3) The assembly block as obtained in step (2) was taken out from the drying box and allowed to cool, and then was placed into a T25 type press supplied by Rockland Research (USA) for high-temperature and high-pressure treatment, wherein the synthesis pressure was 8 GPa, the synthesis temperature was 2000° C. and the holding time was 30 min. Then, the press was cooled and depressurized.

(63) (4) The assembly block was taken out from the press, thereby a novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride, i.e. Gradia BN, was obtained.

(64) The obtained product was observed and analyzed through Themis Z transmission electron microscope. The SAED result demonstrates that the synthesized Gradia BN is a boron nitride material having a novel structure; and the EELS result demonstrates that it is an sp.sup.2-sp.sup.3 hybrid boron nitride. The high resolution transmission electron microscopy image demonstrates that its structural unit is composed of graphite-like structural unit and diamond-like structural unit.

Example 7: Preparation of Gradia BN Using cBN as Boron Nitride Raw Material

(65) The steps (1)-(4) of Example 5 were repeated except that cBN was used as the boron nitride raw material and in step (3) the synthesis pressure was 6 GPa and the synthesis temperature was 1700° C.

(66) The obtained product was observed and analyzed through Themis Z transmission electron microscope. The SAED and EELS results are similar to those shown in FIG. 6. The SAED result demonstrates that the synthesized Gradia BN is a boron nitride material having a novel structure; and the EELS result demonstrates that it is an sp.sup.2-sp.sup.a hybrid boron nitride. The high resolution transmission electron microscopy image demonstrates that its structural unit is composed of graphite-like structural unit and diamond-like structural unit. The crystallographic analysis shows that the sample as obtained contains Gradia-I BN (with a space group of 6 (Pm) or 8 (Cm)) and Gradia-II BN (with a space group of 8 (Cm)).

(67) The product as obtained was further tested by KB-5 BVZ micro-hardness tester and the Vickers hardness test results are shown in FIG. 7. As shown in FIG. 7, the asymptote hardness is about 45 GPa and the maximum hardness is about 50 GPa. FIG. 7 also shows a photograph of the Gradia BN block sample prepared in accordance with Example 7 and a photograph of indentation obtained from the Vickers hardness test under 5 Kg load. By measuring the crack length of the indentation, the fracture toughness of the sample is calculated to be 8-10 MPa.Math.M.sup.1/2.

Example 8: Preparation of Gradia BN Using Sp.SUP.2 .Hybridized hBN as Boron Nitride Raw Material

(68) (1) The raw material hBN was put into dilute hydrochloric acid solution to remove impurities. Then, after hBN was separated from the acid solution, it was rinsed by methanol for several times. The rinsed hBN was then dried, affording the purified hBN raw material. Then, the purified hBN was filled into a pre-pressing mold, and the pre-pressing process was carried out at a pressure of 20 MPa for about 5 minutes using a press to obtain a cylinder body. Then, it was placed into a vacuum hot-pressing sintering furnace for pre-sintering, wherein the pre-sintering temperature was set at 1200° C., the pre-sintering pressure was set at 30 MPa and the pre-sintering time was about 20 min.

(69) (2) The pre-sintered boron nitride raw material body as obtained in step (1) was put into an assembly block, and then the assembly block containing the boron nitride raw material body was put into a drying box for drying wherein the drying temperature was 180° C. and the drying time was 2 h.

(70) (3) The assembly block as obtained in step (2) was taken out from the drying box and allowed to cool, and then was placed into a T25 type press supplied by Rockland Research (USA) for high-temperature and high-pressure treatment, wherein the synthesis pressure was 10 GPa, the synthesis temperature was 1000° C. and the holding time was 60 min. Then, the press was cooled and depressurized.

(71) (4) The assembly block was taken out from the press, thereby a novel sp.sup.2-sp.sup.3 hybrid crystalline boron nitride, i.e. Gradia BN, was obtained.

(72) The obtained product was observed and analyzed through Themis Z transmission electron microscope. The SAED and EELS results are similar to those shown in FIG. 6. The SAED result demonstrates that the synthesized Gradia BN is a boron nitride material having a novel structure; and the EELS result demonstrates that it is an sp.sup.2-sp.sup.3 hybrid boron nitride. The high resolution transmission electron microscopy image demonstrates that its structural unit is composed of graphite-like structural unit and diamond-like structural unit (see FIG. 1). The crystallographic analysis shows that the sample as obtained contains Gradia-I BN (with a space group of 6 (Pm) or 8 (Cm)), Gradia-II BN (with a space group of 8 (Cm)), and Gradia-IV BN (with a space group of 6 (Pm)).

(73) Certain embodiments are described herein, including preferred embodiments known to the inventors, but the scope of the present disclosure is not limited to these embodiments. Of course, equivalent variations on these described embodiments based on structure, shape, principle and the like will become apparent to those of ordinary skill in the art upon reading the foregoing description and will be covered by the scope of the attached claims.

(74) The present disclosure enumerates alternative materials for each component. It is to be understood that the recited list serves only as a representative group and should not be interpreted as an exclusive list. Other materials not mentioned in the disclosure may be used for achieving the purpose of the present disclosure. The embodiments disclosed herein are illustrative of the principles of the embodiments. Thus, by way of example, but not of limitation, alternative embodiments may be utilized in accordance with the teachings herein.

(75) Where a numerical range is disclosed herein, then such a range is continuous, inclusive of both the minimum and maximum values of the range, as well as every value between such minimum and maximum values. Still further, where a range refers to integers, every integer between the minimum and maximum values of such range is included. In addition, where multiple ranges are provided to describe a feature or characteristic, such ranges can be combined. That is to say that, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein. For example, a stated range of from “1 to 10” should be considered to include any and all subranges between the minimum value of 1 and the maximum value of 10. In addition, every point or individual disclosed herein value may serve as a lower or upper limit combined with any other point or individual value or any other lower or upper limit disclosed herein, to form a range not explicitly recited herein, which range will be covered by the protection scope of the attached claims. Moreover, any combination of the above-described elements in all possible variations thereof is contemplated as falling into the protection scope of the attached claims.

(76) In addition, as used herein, the articles “a”, “an” and “the” may include plural referents unless otherwise expressly limited to one-referent, or if it would be obvious to a skilled artisan from the context of the sentence that the article referred to a singular referent.