3D Printed Diamond/Metal Matrix Composite Material and Preparation Method and Use thereof

Abstract

A 3D printed diamond/metal matrix composite material and a preparation method and application thereof are provided. The composite material includes core-shell doped diamond, a metal matrix, and an additive, where the core-shell doped diamond includes a core, a transition layer, a shell, a coating, a porous layer, and a modification layer. The preparation method includes: uniformly mixing the diamond, the metal matrix, and the additive and performing 3D printing according to a 3D CAD slice model to obtain the composite material designed by the model. The metal matrix and the diamond surface of the composite material are mainly metallurgically bound, which can improve the binding strength between the diamond and the metal matrix, thereby improving the use properties of the composite material and a diamond tool. The core-shell doped diamond has good ablation resistance, and can effectively avoid and reduce thermal damage to diamond in a 3D printing forming process.

Claims

1. A method for preparing a 3D printed diamond/metal matrix composite material, comprising the following steps: uniformly mixing a core-shell doped diamond, a metal powder, and an additive to obtain a mixture, placing the mixture in a laser selective melting equipment according to a 3D model of a product, performing a 3D printing to obtain a printed body, and performing an atmospheric pressure heat treatment on the printed body to obtain the 3D printed diamond/metal matrix composite material, wherein the additive is a rare earth element, the core-shell doped diamond is composed of diamond grits and a diamond surface modified layer, and the diamond surface modified layer comprises a diamond transition layer and a doped diamond shell layer from an inside to an outside.

2. The method for preparing the 3D printed diamond/metal matrix composite material according to claim 1, wherein the core-shell doped diamond has a single crystal structure and a particle size of 5 .Math.m-300 .Math.m, the diamond transition layer has a polycrystalline structure and a thickness of 5 nm to 2 .Math.m, the doped diamond shell layer has a thickness of 5 nm to 100 .Math.m and is doped by at least one of a constant doping, a multilayer variable doping, and a gradient doping, with a doping element selected from at least one of boron, nitrogen, phosphorus, and lithium.

3. The method for preparing the 3D printed diamond/metal matrix composite material according to claim 1, wherein the diamond surface modified layer further comprises at least one of a coating, a porous layer, and a modification layer, wherein the coating is a boron film deposited by a chemical vapor deposition on a surface of the doped diamond shell layer, and the boron film deposited by the chemical vapor deposition has a thickness of 10 nm to 200 .Math.m; the porous layer refers to a porous structure prepared by etching the surface of the doped diamond shell layer; and the modification layer is an outermost layer of the diamond surface modified layer, and the modification layer comprises at least one of a metal modification, a carbon material modification, and an organic matter modification.

4. The method for preparing the 3D printed diamond/metal matrix composite material according to claim 1, wherein the metal powder has a particle size of 10 .Math.m-50 .Math.m and is selected from one of a copper powder, an aluminum powder, a silver powder, a nickel powder, a cobalt powder, an iron powder, a titanium powder, a vanadium powder, a tin powder, a magnesium powder, a chromium powder, a zinc powder, an alloy powder of copper, an alloy powder of aluminum, an alloy powder of silver, an alloy powder of nickel, an alloy powder of cobalt, an alloy powder of iron, an alloy powder of titanium, an alloy powder of vanadium, an alloy powder of tin, an alloy powder of magnesium, an alloy powder of chromium, and an alloy powder of zinc; and the rare earth element is selected from at least one of lanthanum, cerium, neodymium, europium, gadolinium, dysprosium, holmium, ytterbium, lutetium, yttrium, and scandium.

5. The method for preparing the 3D printed diamond/metal matrix composite material according to claim 1, wherein a mass fraction of the core-shell doped diamond in the mixture is 5%-60%, and a mass fraction of the additive in the mixture is 0.05%-1%.

6. The method for preparing the 3D printed diamond/metal matrix composite material according to claim 1, wherein the 3D printing is performed in an argon atmosphere at a power of 100 W-800 W, a scanning speed of 100 mm/s-800 mm/s, a scanning distance of 0.04 mm-0.2 mm, and a temperature field of 673 K-1273 K, and the metal powder has a thickness of less than or equal to 0.6 mm, and the 3D printing is a laser printing or an electron beam printing.

7. The method for preparing the 3D printed diamond/metal matrix composite material according to claim 1, wherein the atmospheric pressure heat treatment is performed at a vacuum degree of 10 pa-100 pa, a heating temperature of 200° C.-800° C., a gas pressure of 2 Mpa-15 Mpa, and a pressure holding time of 30 min-300 min.

8. The method for preparing the 3D printed diamond/metal matrix composite material according to claim 1, wherein the 3D printed diamond/metal matrix composite material has a density of 70%-98%, and wherein in the 3D printed diamond/metal matrix composite material, a volume fraction of the core-shell doped diamond is not less than 5%.

9. A 3D printed diamond/metal matrix composite material prepared by the method according to claim 1.

10. A method of use of the 3D printed diamond/metal matrix composite material prepared by the method according to claim 1 as a packaging material or a wear-resistant material.

11. The 3D printed diamond/metal matrix composite material according to claim 9, wherein in a process of preparing the 3D printed diamond/metal matrix composite material, the core-shell doped diamond has a single crystal structure and a particle size of 5 .Math.m-300 .Math.m, the diamond transition layer has a polycrystalline structure and a thickness of 5 nm to 2 .Math.m, the doped diamond shell layer has a thickness of 5 nm to 100 .Math.m and is doped by at least one of a constant doping, a multilayer variable doping, and a gradient doping, with a doping element selected from at least one of boron, nitrogen, phosphorus, and lithium.

12. The 3D printed diamond/metal matrix composite material according to claim 9, wherein in a process of preparing the 3D printed diamond/metal matrix composite material, the diamond surface modified layer further comprises at least one of a coating, a porous layer, and a modification layer, wherein the coating is a boron film deposited by a chemical vapor deposition on a surface of the doped diamond shell layer, and the boron film deposited by the chemical vapor deposition has a thickness of 10 nm to 200 um; the porous layer refers to a porous structure prepared by etching the surface of the doped diamond shell layer; and the modification layer is an outermost layer of the diamond surface modified layer, and the modification layer comprises at least one of a metal modification, a carbon material modification, and an organic matter modification.

13. The 3D printed diamond/metal matrix composite material according to claim 9, wherein in a process of preparing the 3D printed diamond/metal matrix composite material, the metal powder has a particle size of 10 .Math.m-50 .Math.m and is selected from one of a copper powder, an aluminum powder, a silver powder, a nickel powder, a cobalt powder, an iron powder, a titanium powder, a vanadium powder, a tin powder, a magnesium powder, a chromium powder, a zinc powder, an alloy powder of copper, an alloy powder of aluminum, an alloy powder of silver, an alloy powder of nickel, an alloy powder of cobalt, an alloy powder of iron, an alloy powder of titanium, an alloy powder of vanadium, an alloy powder of tin, an alloy powder of magnesium, an alloy powder of chromium, and an alloy powder of zinc; and the rare earth element is selected from at least one of lanthanum, cerium, neodymium, europium, gadolinium, dysprosium, holmium, ytterbium, lutetium, yttrium, and scandium.

14. The 3D printed diamond/metal matrix composite material according to claim 9, wherein in a process of preparing the 3D printed diamond/metal matrix composite material, a mass fraction of the core-shell doped diamond in the mixture is 5%-60%, and a mass fraction of the additive in the mixture is 0.05%-1%.

15. The 3D printed diamond/metal matrix composite material according to claim 9, wherein in a process of preparing the 3D printed diamond/metal matrix composite material, the 3D printing is performed in an argon atmosphere at a power of 100 W-800 W, a scanning speed of 100 mm/s-800 mm/s, a scanning distance of 0.04 mm-0.2 mm, and a temperature field of 673 K-1273 K, and the metal powder has a thickness of less than or equal to 0.6 mm, and the 3D printing is a laser printing or an electron beam printing.

16. The 3D printed diamond/metal matrix composite material according to claim 9, wherein in a process of preparing the 3D printed diamond/metal matrix composite material, the atmospheric pressure heat treatment is performed at a vacuum degree of 10 pa-100 pa, a heating temperature of 200° C.-800° C., a gas pressure of 2 Mpa-15 Mpa, and a pressure holding time of 30 min-300 min.

17. The 3D printed diamond/metal matrix composite material according to claim 9, wherein the 3D printed diamond/metal matrix composite material has a density of 70%-98%, and wherein in the 3D printed diamond/metal matrix composite material, a volume fraction of the core-shell doped diamond is not less than 5%.

18. The method of use of the 3D printed diamond/metal matrix composite material according to claim 10, wherein in a process of preparing the 3D printed diamond/metal matrix composite material, the core-shell doped diamond has a single crystal structure and a particle size of 5 .Math.m-300 .Math.m, the diamond transition layer has a polycrystalline structure and a thickness of 5 nm to 2 .Math.m, the doped diamond shell layer has a thickness of 5 nm to 100 .Math.m and is doped by at least one of a constant doping, a multilayer variable doping, and a gradient doping, with a doping element selected from at least one of boron, nitrogen, phosphorus, and lithium.

19. The method of use of the 3D printed diamond/metal matrix composite material according to claim 10, wherein in a process of preparing the 3D printed diamond/metal matrix composite material, the diamond surface modified layer further comprises at least one of a coating, a porous layer, and a modification layer, wherein the coating is a boron film deposited by a chemical vapor deposition on a surface of the doped diamond shell layer, and the boron film deposited by the chemical vapor deposition has a thickness of 10 nm to 200 .Math.m; the porous layer refers to a porous structure prepared by etching the surface of the doped diamond shell layer; and the modification layer is an outermost layer of the diamond surface modified layer, and the modification layer comprises at least one of a metal modification, a carbon material modification, and an organic matter modification.

20. The method of use of the 3D printed diamond/metal matrix composite material according to claim 10, wherein in a process of preparing the 3D printed diamond/metal matrix composite material, the metal powder has a particle size of 10 .Math.m-50 .Math.m and is selected from one of a copper powder, an aluminum powder, a silver powder, a nickel powder, a cobalt powder, an iron powder, a titanium powder, a vanadium powder, a tin powder, a magnesium powder, a chromium powder, a zinc powder, an alloy powder of copper, an alloy powder of aluminum, an alloy powder of silver, an alloy powder of nickel, an alloy powder of cobalt, an alloy powder of iron, an alloy powder of titanium, an alloy powder of vanadium, an alloy powder of tin, an alloy powder of magnesium, an alloy powder of chromium, and an alloy powder of zinc; and the rare earth element is selected from at least one of lanthanum, cerium, neodymium, europium, gadolinium, dysprosium, holmium, ytterbium, lutetium, yttrium, and scandium.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

Example 1

Preparation of core-shell doped diamond

[0040] Using 150 .Math.m single crystal diamond grits as a raw material, a polycrystalline diamond transition layer was deposited on the surfaces of the diamond grits by chemical deposition in the presence of a fed atmosphere of CH.sub.4 and H.sub.2 in a mass flow ratio of 2:98 twice for 20 min each time, and finally a polycrystalline diamond transition layer with a maximum thickness of 400 nm was obtained.

[0041] Then, a doped diamond shell layer was grown on the surface of the polycrystalline diamond transition layer by hot wire chemical vapor deposition to obtain a diamond reinforcement. The deposition was performed at a hot wire distance of 10 mm, a hot wire thickness of 0.5 mm, a growth temperature of 850° C., and a deposition pressure of 3 KPa, and a diamond film having a thickness of 2 .Math.m was prepared by controlling the deposition time. The chemical vapor deposition was performed in the presence of a fed gas of CH.sub.4, H.sub.2 and B.sub.2H.sub.6 in a mass flow ratio of 2:97:1 at a growth pressure of 3 Kpa twice. After each growth, carrier particles were taken out and shaken before continuing the growth, and the growth lasted for 1 h each time.

[0042] The core-shell doped diamond was compounded with metal by 3D printing. The core-shell doped diamond, iron powder, nickel powder and lanthanum powder were mixed uniformly to obtain a mixture, where the mass ratio of the core-shell doped diamond to the sum of iron powder and nickel powder to the lanthanum powder was 30%:69.9%:0.1%.

[0043] The mixture was placed in laser selective melting equipment according to a 3D model of a product, and 3D printing was performed in an argon atmosphere at a laser power of 150 W, a scanning speed of 700 mm/s, a scanning distance of 0.06 mm, a temperature field of 773 K, and a powder thickness of 0.4 mm to obtain a 3D printed body. Then, the 3D printed body was subjected to atmospheric pressure heat treatment in a nitrogen atmosphere at a vacuum degree of lower than 100 pa, a heating temperature of 300° C., a gas pressure of 6 Mpa, and a pressure holding time of 1 h to obtain the diamond/metal matrix composite material.

[0044] The prepared diamond/metal matrix composite material in the present example had a density of 70%, and in the prepared diamond/metal matrix composite material, the volume fraction of the core-shell doped diamond was 30%.

[0045] The prepared composite material had a hardness of greater than or equal to 90 HRB, a service life of 1.5 times or more than that of an abrasive tool made of a superhard material prepared by the traditional technology, a wear ratio increased by 60% or more, and heat resistance of 800° C. or above.

Example 2

Preparation of core-shell doped diamond

[0046] Using 150 .Math.m single crystal diamond grits as a raw material, a polycrystalline diamond transition layer was deposited on the surfaces of the diamond grits by chemical deposition in the presence of a fed atmosphere of CH.sub.4 and H.sub.2 in a mass flow ratio of 2:98 twice for 20 min each time, and finally a polycrystalline diamond transition layer with a maximum thickness of 400 nm was obtained.

[0047] Then, a doped diamond shell layer was grown on the surface of the polycrystalline diamond transition layer by hot wire chemical vapor deposition to obtain a diamond reinforcement. The deposition was performed at a hot wire distance of 10 mm, a hot wire thickness of 0.5 mm, a growth temperature of 850° C., and a deposition pressure of 3 KPa, and a diamond film having a thickness of 3 .Math.m was prepared by controlling the deposition time. The chemical vapor deposition was performed in three periods for growth deposition, where in the first period of deposition, the mass flow ratio of CH.sub.4 to H.sub.2 to B.sub.2H.sub.6 in the fed gas was 2:97:0.15; in the second period of deposition, the mass flow ratio of CH.sub.4 to H.sub.2 to B.sub.2H.sub.6 in the fed gas was 2:97:0.35 sccm; and in the third period of deposition, the mass flow ratio of CH.sub.4 to H.sub.2 to B.sub.2H.sub.6 in the fed gas was 2:97:0.55. The growth pressure was 3 Kpa. After each growth, carrier particles were taken out and shaken before continuing the growth, and the growth lasted for 1 h each time.

[0048] The core-shell doped diamond was compounded with metal by 3D printing. The core-shell doped diamond, iron powder, nickel powder, cobalt powder and cerium powder were mixed uniformly to obtain a mixture, where the mass ratio of the core-shell doped diamond to the sum of iron powder, nickel powder and cobalt powder to the cerium powder was 35%:64.9%:0.1%.

[0049] The mixture was placed in laser selective melting equipment according to a 3D model of a product, and 3D printing was performed in an argon atmosphere at a laser power of 450 W, a scanning speed of 300 mm/s, a scanning distance of 0.05 mm, a temperature field of 773 K, and a powder thickness of 0.4 mm to obtain a 3D printed body. Then, the 3D printed body was subjected to atmospheric pressure heat treatment in a nitrogen atmosphere at a vacuum degree of lower than 100 pa, a heating temperature of 200° C., a gas pressure of 6 Mpa, and a pressure holding time of 1 h to obtain the diamond/metal matrix composite material.

[0050] The prepared diamond/metal matrix composite material in the present example had a density of 90%, and in the prepared diamond/metal matrix composite material, the volume fraction of the core-shell doped diamond was 35%.

[0051] The diamond/metal matrix composite material tested had a hardness of greater than or equal to 120 HRB, a service life of 2 times or more than that of an abrasive tool made of a superhard material prepared by the traditional technologies (e.g. electroplating, hot pressing sintering, non-pressure infiltration and high-temperature brazing), a wear ratio increased by 80% above, and heat resistance of 800° C. or above.

Example 3

Preparation of core-shell doped diamond

[0052] Using 200 .Math.m single crystal diamond grits as a raw material, a polycrystalline diamond transition layer was deposited on the surfaces of the diamond grits by chemical deposition in the presence of a fed atmosphere of CH.sub.4 and H.sub.2 in a mass flow ratio of 2:98 twice for 20 min each time, and finally a polycrystalline diamond transition layer with a maximum thickness of 400 nm was obtained.

[0053] Then, a doped diamond shell layer was grown on the surface of the polycrystalline diamond transition layer by hot wire chemical vapor deposition to obtain a diamond reinforcement. The deposition was performed at a hot wire distance of 10 mm, a hot wire thickness of 0.5 mm, a growth temperature of 850° C., and a deposition pressure of 3 KPa, and a diamond film having a thickness of 2 .Math.m was prepared by controlling the deposition time. The chemical vapor deposition was performed in the presence of a fed gas of CH.sub.4, H.sub.2 and B.sub.2H.sub.6 in a mass flow ratio of 2:97:1 at a growth pressure of 3 Kpa twice. After each growth, carrier particles were taken out and shaken before continuing the growth, and the growth lasted for 1 h each time.

[0054] A boron film was deposited by chemical vapor deposition on the surface of the doped diamond shell layer at a hot wire distance of 50 mm, a temperature of 800° C., and a deposition pressure of 3 KPa, and a diamond film having a thickness of 50 .Math.m was prepared by controlling the deposition time. The chemical vapor deposition was performed in the presence of a fed gas of H.sub.2 and B.sub.2H.sub.6 in a mass flow ratio of 95:5 twice. After each deposition, carrier particles were taken out and shaken before continuing the growth, and the growth lasted for 10 h each time.

Compounding of the core-shell doped diamond with metal by 3D printing

[0055] The core-shell doped diamond, Cu—B alloy powder and lanthanum powder were mixed uniformly to obtain a mixture, and the mass ratio of the core-shell doped diamond to the Cu-B alloy powder to the lanthanum powder was 50%:49.9%:0.1%.

[0056] The mixture was placed in laser selective melting equipment according to a 3D model of a product, and 3D printing was performed in an argon atmosphere at a laser power of 400 W, a scanning speed of 300 mm/s, a scanning distance of 0.045 mm, a temperature field of 1073 K, and a powder thickness of 0.5 mm to obtain a 3D printed body. Then, the 3D printed body was subjected to atmospheric pressure heat treatment in an argon atmosphere at a vacuum degree of lower than 100 pa, a heating temperature of 400° C., a gas pressure of 8 Mpa, and a pressure holding time of 1 h to obtain the diamond/metal matrix composite material.

[0057] The prepared diamond/metal matrix composite material in the present example had a density of 85%, and in the prepared diamond/metal matrix composite material, the volume fraction of the core-shell doped diamond was 50%.

[0058] The diamond/metal matrix composite material tested had a thermal conductivity of 830 W/mK, a thermal expansion coefficient of 5×10.sup.-6/K, a density of less than 6 g/cm.sup.3, a bending resistance of 450 Mpa, and a surface roughness of less than 3.2 .Math.m, and could be used at a temperature ranging from -50 to 500° C.

Example 4

Preparation of a diamond reinforcement

[0059] Using 200 .Math.m single crystal diamond grits as a raw material, a polycrystalline diamond transition layer was deposited on the surfaces of the diamond grits by chemical deposition in the presence of a fed atmosphere of CH.sub.4 and H.sub.2 in a mass flow ratio of 2:98 twice for 20 min each time, and finally a polycrystalline diamond transition layer with a maximum thickness of 400 nm was obtained.

[0060] Then, a doped diamond shell layer was grown on the surface of the polycrystalline diamond transition layer by hot wire chemical vapor deposition to obtain a diamond reinforcement. The deposition was performed at a hot wire distance of 10 mm, a hot wire thickness of 0.5 mm, a growth temperature of 850° C., and a deposition pressure of 3 KPa, and a diamond film having a thickness of 3 .Math.m was prepared by controlling the deposition time. The chemical vapor deposition was performed in three periods for growth deposition, where in the first period of deposition, the mass flow ratio of CH.sub.4 to H.sub.2 to B.sub.2H.sub.6 in the fed gas was 2:97:0.15; in the second period of deposition, the mass flow ratio of CH.sub.4 to H.sub.2 to B.sub.2H.sub.6 in the fed gas was 2:97:0.35 sccm; and in the third period of deposition, the mass flow ratio of CH.sub.4 to H.sub.2 to B.sub.2H.sub.6 in the fed gas was 2:97:0.55. The growth pressure was 3 Kpa. After each growth, carrier particles were taken out and shaken before continuing the growth, and the growth lasted for 1 h each time.

[0061] Then, the doped diamond shell layer was etched into a porous structure by plasma in a tube furnace with a plasma device at a temperature of 800° C. and a vacuum degree of n 0 pa or below in a hydrogen or oxygen atmosphere with a gas flow rate of 35 sccm for 60 min to obtain a porous modified layer.

[0062] Then, metal modification was performed by the physical vapor deposition technology in a high-purity argon atmosphere with a flow rate of 30 sccm, at a vacuum degree of 0.5-1 Pa, a temperature of 473 KK and a power of 200 W for a sputtering time of 30 min to obtain a thickness of 3 .Math.m.

Compounding of the core-shell doped diamond with metal by 3D printing

[0063] The core-shell doped diamond, Cu—Zr alloy powder and lanthanum powder were mixed uniformly to obtain a mixture, and the mass ratio of the core-shell doped diamond to the Cu-Zr alloy powder to the lanthanum powder was 50%:49.9%:0.1%.

[0064] The mixture was placed in laser selective melting equipment according to a 3D model of a product, and 3D printing was performed in an argon atmosphere at a laser power of 400 W, a scanning speed of 400 mm/s, a scanning distance of 0.045 mm, a temperature field of 1073 K, and a powder thickness of 0.5 mm to obtain a 3D printed body. Then, the 3D printed body was subjected to atmospheric pressure heat treatment in an argon atmosphere at a vacuum degree of lower than 100 pa, a heating temperature of 300° C., a gas pressure of 10 Mpa, and a pressure holding time of 2 h to obtain the diamond/metal matrix composite material.

[0065] The prepared diamond/metal matrix composite material in the present example had a density of 95%, and in the prepared diamond/metal matrix composite material, the volume fraction of the core-shell doped diamond was 50%.

[0066] The diamond/metal matrix composite material tested had a thermal conductivity of 900 W/mK, a thermal expansion coefficient of 4.8×10.sup.-6/K,

[0067] a density of less than 6 g/cm.sup.3, a bending resistance of 580 Mpa, and a surface roughness of less than or equal to 3.2 .Math.m, and could be used at a temperature ranging from -50 to 500° C.

Comparative example 1

[0068] Other conditions were the same as in Example 1, except that no rare earth elements were added. The interface of the composite material prepared was easily debonded and cracked under the interaction of heating and cooling, and the binding performance was insufficient, resulting in lots of defects at the interface, and resulting in a decline in the overall properties of the material and low thermal conductivity during use.

Comparative example 2

[0069] Other conditions were the same as in Example 1, except that no diamond transition layer was formed in the core-shell doped diamond. The diamond/metal matrix composite material without the transition layer had weak binding strength, low wettability, easy oxidation on the surface, easy carbonization at high temperature, and low ablation resistance.

Comparative example 3

[0070] Other conditions were the same as in Example 1, except that atmosphere pressure heating treatment was not performed after 3D printing. The obtained material has internal stress, deformation and cracks, and a microstructure which is not delicate.