CN111056842A - Micro-nano polycrystalline diamond composite material and preparation method thereof - Google Patents

Micro-nano polycrystalline diamond composite material and preparation method thereof Download PDF

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CN111056842A
CN111056842A CN201911354946.7A CN201911354946A CN111056842A CN 111056842 A CN111056842 A CN 111056842A CN 201911354946 A CN201911354946 A CN 201911354946A CN 111056842 A CN111056842 A CN 111056842A
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nano
polycrystalline diamond
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composite material
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李艳国
邹芹
王明智
赵玉成
代利峰
王志伟
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Yanshan University
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Abstract

The invention discloses a micro-nano polycrystalline diamond composite material and a preparation method thereof, wherein the components comprise carbon nano-onions and micro-diamonds; the mass percent of the micro diamond is 20-50 wt.%, and the balance is carbon nano shallot; the micro-nano polycrystalline diamond composite material has the Vickers hardness of 30-200 GPa. The preparation method comprises the following steps: annealing the detonation nano diamond powder to prepare carbon nano shallots; adding micro-diamond grains for mixing, wherein the mass percent of the micro-diamond grains is 20-50 wt.%; filling a mixture formed by the micro-diamond and the carbon nano-onion into a WC hard alloy die for prepressing, wherein the prepressing pressure is 400-600 MPa and the prepressing time is 10-30 s; and putting the prepressed sample into a die for high-temperature high-pressure sintering to prepare the micro-nano polycrystalline diamond composite material. The Vickers hardness of the micro-nano polycrystalline diamond is nearly doubled than that of common PCD, and the performance is obviously improved.

Description

Micro-nano polycrystalline diamond composite material and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials, in particular to a micro-nano polycrystalline diamond composite material and a preparation method thereof.
Background
At present, polycrystalline diamond (PCD) has high hardness and wear resistance, overcomes the defects of single crystal diamond anisotropy and {111} crystal face dissociation damage, and is widely applied to the fields of aerospace, electronics, construction, gem processing, petroleum drilling, geological exploration and the like.
Wangming et al adopts nano onion-carbon as a raw material, synthesizes polycrystalline diamond by a cubic press at the temperature of 2-6 GPa/1000-1600 ℃/for 1-6 min, has compact blocks, the Vickers hardness of HV 45-61 GPa, and the grain size of a sintered body of less than 20nm, overcomes the defect that the performance of PCD is reduced by weak phases in PCD synthesized by the prior art, and synthesizes PCD with high hardness under the condition of lower sintering; celery is contained in the Chinese herbal medicine; zhao Yucheng. The method for preparing the polycrystalline diamond sintered body by the nano onion-carbon at high temperature and high pressure comprises the following steps: cn101723358a. university of yanshan university, published 6/9/2010 ].
Wangming et al adopts OLC and micron diamond, and utilizes a cubic press to synthesize the polycrystalline diamond at the temperature of 4-6.5 GPa/1000-1600 ℃/1-15 min, the obtained polycrystalline diamond sintered body has smooth surface and compact blocks, the Vickers hardness reaches HV41-70GPa [ Wangming, celery, Zhaoyuan, etc.. the method for preparing the polycrystalline diamond by using the nano onion-carbon + micron diamond: cn103274398a, university of yanshan, published 2013, 9/4/h.
The Tian Yongjun et al invent a nanometer twin crystal diamond block material with ultrahigh hardness and a preparation method thereof, adopts OLC with high density defect to synthesize nanometer twin crystal diamond (nt-diamond) under the condition of 18-25 GPa/1850-; the Knoop hardness is 140-240 GPa; the width of the twin crystal is 1-15 nm, and the hardness of the twin crystal is far higher than that of diamond single crystal and superhard polycrystalline diamond [ Tian Yongjun; yellow weights; it is beneficial to the multi-purpose. The ultra-high hardness nanometer twin crystal diamond block material and the preparation method thereof are as follows: cn104209062a, yanshan university, published 12 months and 17 days 2014 ].
The phase transition behavior of OLC was studied by Tanghuo under the condition of 10-25GPa/1800 ℃. The results demonstrate that the OLC to diamond transformation is a martensitic transformation process similar to the graphite to diamond transformation. The occurrence of the phase transition causes mutual sliding of the OLC (002) planes. However, the sliding of the (002) plane is limited by the closed continuous carbon shell layer, resulting in the generation of stress, and the formation of twin-crystal diamond is the result of cumulative stress release [ tang tiger, research on the synthesis of nano polycrystalline diamond and the high-temperature and high-pressure phase transformation mechanism of carbon nano onion [ D ]. qinhuang island: university of Yanshan, 2018 ]. The PCD synthesized by taking the carbon nano-Onion (OLC) as a precursor requires extremely high pressure and temperature conditions (P is more than or equal to 18GPa, T is more than or equal to 2300 ℃), has high requirements on equipment and high cost, and the synthesized PCD is difficult to apply due to the fact that the size is less than 3mm at most.
Disclosure of Invention
In view of the above-mentioned problems, a micro-nano polycrystalline diamond composite material and a method for preparing the same are provided. The method takes a mixture of carbon nano-Onions (OLC) and micro-diamonds (MD) prepared by an annealing method as a raw material, adopts high-temperature and high-pressure (8-25 GPa/1600-2150 ℃/heat preservation time for 5-60 min) sintering to prepare the micro-nano polycrystalline diamond composite material, utilizes the micro-diamonds to balance the internal pressure loss of a sintered body and serve as seed crystals to promote the growth of the diamonds, reduces the sintering conditions, and obtains the high-hardness micro-nano polycrystalline diamond composite material.
The technical means adopted by the invention are as follows:
a micro-nano polycrystalline diamond composite material, the components of which comprise carbon nano-onions and micro-diamonds;
the mass percent of the micro diamond is 20-50 wt.%, and the balance is carbon nano shallot.
The average particle size of the carbon nano-onions is about 5nm, and the particle size value range of the carbon nano-onions is 2-13 nm;
the micron diamond is a crushed material, the granularity of the micron diamond is 0.5-5 microns, and the purity of the micron diamond is 99%.
The micro-nano polycrystalline diamond composite material has the Vickers hardness of 30-200 GPa.
A preparation method of a micro-nano polycrystalline diamond composite material comprises the following steps:
s1, annealing detonation nano diamond powder with average grain size of 5nm, wherein the vacuum degree in the annealing treatment is 1-1.0 multiplied by 10-2Pa, annealing temperature of 900-1600 ℃, and keeping the temperature for 0-2 h after annealing to prepare the carbon nano-shallot with the average grain size of 5 nm;
s2, adding micron diamond grains into the carbon nano shallot prepared in the step S1, and mixing, wherein the mass percent of the micron diamond grains is 20-50 wt%;
s3, filling a mixture formed by the micron diamond and the carbon nano-onion into a WC hard alloy die for prepressing, wherein the prepressing pressure is 400-600 MPa and the prepressing pressure is 10-30S;
and S4, putting the pre-pressed sample into a mould, and sintering at high temperature and high pressure to obtain the micro-nano polycrystalline diamond composite material.
The WC cemented carbide mold in the step S3 uses LaCaO3As heat insulating material, Re as heating body, pyrophyllite as sealing material, MgO or Al2O3As a pressure transmission medium, a W-Re thermocouple measures the temperature.
The high-temperature high-pressure sintering process in the step S4 includes:
firstly, slowly applying pressure to a pre-pressed sample within 10-24h to 8-25 GPa; and then, heating the temperature to 1600-2150 ℃ from room temperature at a heating rate of 10-30 ℃/min, preserving the temperature for 5-60 min, cooling the temperature along with the furnace to obtain a blank, and carrying out surface grinding and deburring treatment on the prepared blank to obtain the micro-nano polycrystalline diamond composite material.
The invention has the following advantages:
1. the micro-nano polycrystalline diamond composite material has higher Vickers hardness which is 20-200GPa, and the Vickers hardness of the micro-nano polycrystalline diamond composite material is gradually improved along with the improvement of sintering pressure and sintering temperature. The Vickers hardness of the micro-nano polycrystalline diamond is nearly doubled than that of common PCD, and the performance is obviously improved.
2. The micro-nano polycrystalline diamond of the present invention contains a large amount of twin structures and stacking faults therein, which are the reasons for the increased hardness thereof.
3. The invention balances the internal pressure loss of the sintered body by using the micron diamond, promotes the growth of the diamond as the seed crystal, reduces the sintering condition of OLC, and solves the problem of high sintering condition of OLC because the sintered body has higher hardness.
For the reasons, the invention can be widely popularized in the fields of composite materials and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an X-ray diffraction spectrum of a micro-nano-scale polycrystalline diamond composite material in example 5 of the present invention.
Fig. 2 is a Raman spectroscopy (Raman) graph of the micro-nano-scale polycrystalline diamond composite in example 5 of the present invention.
Fig. 3 is an X-ray diffraction spectrum of the micro-nano-scale polycrystalline diamond composite in example 6 of the present invention.
Fig. 4 is a Raman spectroscopy (Raman) graph of the micro-nano-scale polycrystalline diamond composite in example 6 of the present invention.
Fig. 5 is an X-ray diffraction spectrum of the micro-nano-scale polycrystalline diamond composite in example 7 of the present invention.
Fig. 6 is a Raman spectroscopy (Raman) graph of the micro-nano-scale polycrystalline diamond composite in example 7 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A micro-nano polycrystalline diamond composite material, the components of which comprise carbon nano-onions and micro-diamonds;
the mass percent of the micro diamond is 20-50 wt.%, and the balance is carbon nano shallot.
The average particle size of the carbon nano shallots is 5 nm;
the micron diamond is a crushed material, the granularity of the micron diamond is 0.5-5 microns, and the purity of the micron diamond is 99%.
The micro-nano polycrystalline diamond composite material has the Vickers hardness of 30-200 GPa.
Example 2
A preparation method of a micro-nano polycrystalline diamond composite material comprises the following steps:
s1, annealing detonation nano diamond powder with the average grain size of 5nm, wherein the vacuum degree is 1Pa, the annealing temperature is 900 ℃, and the annealing is not carried out, so that carbon nano shallots with the average grain size of 5nm are prepared;
s2, 8mg of carbon nano-onions are selected, 2mg of micron diamond grains are added into the carbon nano-onions, and mixing is carried out;
s3, filling a mixture formed by the micron diamond and the carbon nano-onion into a WC hard alloy die for prepressing, wherein the prepressing pressure is 400MPa and the prepressing pressure is 10S;
and S4, putting the pre-pressed sample into a mould, and sintering at high temperature and high pressure to obtain the micro-nano polycrystalline diamond composite material.
Preferably, the WC cemented carbide die uses laccao in the step S33As heat insulating material, Re as heating body, pyrophyllite as sealing material, MgO or Al2O3As a pressure transmission medium, a W-Re thermocouple measures the temperature.
Preferably, the high-temperature high-pressure sintering process in step S4 is as follows:
firstly, slowly applying pressure to a pre-pressed sample within 10h to 8 GPa; and then, heating the temperature from room temperature to 1600 ℃ at the heating rate of 10 ℃/min, preserving the temperature for 5min, cooling the blank along with the furnace to prepare a blank, and carrying out surface grinding and deburring treatment on the prepared blank to obtain the micro-nano polycrystalline diamond composite material.
And grinding and polishing the micro-nano polycrystalline diamond composite material sample after high-pressure sintering, and then carrying out tissue and performance detection to obtain a sintered block with the Vickers hardness value of 30.45 GPa.
Example 3
A preparation method of a micro-nano polycrystalline diamond composite material comprises the following steps:
s1, annealing detonation nano diamond powder with average grain size of 5nm, wherein the vacuum degree in the annealing treatment is 1.0 × 10-1Pa, annealing temperature 1000 ℃, and keeping the temperature for 1h after annealing to prepare the carbon nano-shallot with the average grain size of 5 nm;
s2, selecting 7g of carbon nano-onions, adding 2g of micron diamond grains, and mixing;
s3, filling a mixture formed by the micron diamond and the carbon nano-onion into a WC hard alloy die for prepressing, wherein the prepressing pressure is 500MPa and the prepressing time is 15S;
and S4, putting the pre-pressed sample into a mould, and sintering at high temperature and high pressure to obtain the micro-nano polycrystalline diamond composite material.
Preferably, the WC cemented carbide die uses laccao in the step S33As heat insulating material, Re as heating body, pyrophyllite as sealing material, MgO or Al2O3As a medium for transmitting the pressure,and measuring the temperature by a W-Re thermocouple.
Preferably, the high-temperature high-pressure sintering process in step S4 is as follows:
firstly, slowly applying pressure to a pre-pressed sample within 10h to 10 GPa; and then, heating the temperature from room temperature to 1700 ℃ at the heating rate of 20 ℃/min, preserving the temperature for 15min, cooling the blank along with the furnace to prepare a blank, and carrying out surface grinding and deburring treatment on the prepared blank to obtain the micro-nano polycrystalline diamond composite material.
And grinding and polishing the micro-nano polycrystalline diamond composite material sample after high-pressure sintering, and then carrying out tissue and performance detection, wherein the Vickers hardness value of the obtained sintered block is 46.24 GPa.
Example 4
A preparation method of a micro-nano polycrystalline diamond composite material comprises the following steps:
s1, annealing detonation nano diamond powder with average grain size of 5nm, wherein the vacuum degree in the annealing treatment is 1.0 × 10-1Pa, annealing temperature 1100 ℃, and keeping the temperature for 2h after annealing to prepare the carbon nano-shallot with the average grain size of 5 nm;
s2, selecting 6mg of carbon nano-onions, adding 4mg of micron diamond grains, and mixing;
s3, filling a mixture formed by the micron diamond and the carbon nano-onion into a WC hard alloy die for prepressing, wherein the prepressing pressure is 600MPa and the prepressing time is 20S;
and S4, putting the pre-pressed sample into a mould, and sintering at high temperature and high pressure to obtain the micro-nano polycrystalline diamond composite material.
Preferably, the WC cemented carbide die uses laccao in the step S33As heat insulating material, Re as heating body, pyrophyllite as sealing material, MgO or Al2O3As a pressure transmission medium, a W-Re thermocouple measures the temperature.
Preferably, the high-temperature high-pressure sintering process in step S4 is as follows:
firstly, slowly applying pressure to a pre-pressed sample within 11h to 12 GPa; and then heating the mixture from room temperature to 1800 ℃ at the heating rate of 30 ℃/min, preserving the heat for 30min, cooling the mixture along with the furnace to prepare a blank, and grinding and deburring the surface of the prepared blank to obtain the micro-nano polycrystalline diamond composite material.
And grinding and polishing the micro-nano polycrystalline diamond composite material sample after high-pressure sintering, and then carrying out tissue and performance detection, wherein the Vickers hardness value of the obtained sintered block is 65.01 GPa.
Example 5
A preparation method of a micro-nano polycrystalline diamond composite material comprises the following steps:
s1, annealing detonation nano diamond powder with average grain size of 5nm, wherein the vacuum degree in the annealing treatment is 1.0 × 10-2Pa, the annealing temperature is 1200 ℃, and the temperature is not preserved after annealing, so that the carbon nano-shallot with the average grain size of 5nm is prepared;
s2, selecting 5mg of carbon nano-onions, adding 5mg of micron diamond grains, and mixing;
s3, filling a mixture formed by the micron diamond and the carbon nano-onion into a WC hard alloy die for prepressing, wherein the prepressing pressure is 400MPa and the prepressing pressure is 25S;
and S4, putting the pre-pressed sample into a mould, and sintering at high temperature and high pressure to obtain the micro-nano polycrystalline diamond composite material.
Preferably, the WC cemented carbide die uses laccao in the step S33As heat insulating material, Re as heating body, pyrophyllite as sealing material, MgO or Al2O3As a pressure transmission medium, a W-Re thermocouple measures the temperature.
Preferably, the high-temperature high-pressure sintering process in step S4 is as follows:
firstly, slowly applying pressure to a pre-pressed sample within 13h to 14 GPa; and then heating the mixture from room temperature to 1900 ℃ at the heating rate of 10 ℃/min, preserving the heat for 60min, cooling the mixture along with the furnace to prepare a blank, and grinding and deburring the surface of the prepared blank to obtain the micro-nano polycrystalline diamond composite material.
And grinding and polishing the micro-nano polycrystalline diamond composite material sample after high-pressure sintering, and then carrying out tissue and performance detection to obtain a sintered block with the Vickers hardness value of 97.86 GPa. An X-ray diffraction spectrum of the micro-nano-scale polycrystalline diamond composite material is shown in fig. 1, and a Raman chart of the micro-nano-scale polycrystalline diamond composite material is shown in fig. 2.
Example 6
A preparation method of a micro-nano polycrystalline diamond composite material comprises the following steps:
s1, annealing detonation nano diamond powder with average grain size of 5nm, wherein the vacuum degree in the annealing treatment is 1.0 × 10-2Pa, annealing temperature 1300 ℃, and keeping the temperature for 1h after annealing to prepare the carbon nano-shallot with the average grain size of 5 nm;
s2, 8mg of carbon nano-onions are selected, 2mg of micron diamond grains are added into the carbon nano-onions, and mixing is carried out;
s3, filling a mixture formed by the micron diamond and the carbon nano-onion into a WC hard alloy die for prepressing, wherein the prepressing pressure is 500MPa and the prepressing time is 30S;
and S4, putting the pre-pressed sample into a mould, and sintering at high temperature and high pressure to obtain the micro-nano polycrystalline diamond composite material.
Preferably, the WC cemented carbide die uses laccao in the step S33As heat insulating material, Re as heating body, pyrophyllite as sealing material, MgO or Al2O3As a pressure transmission medium, a W-Re thermocouple measures the temperature.
Preferably, the high-temperature high-pressure sintering process in step S4 is as follows:
firstly, slowly applying pressure to a pre-pressed sample to 16GPa within 15 h; and then, heating the temperature from room temperature to 2000 ℃ at the heating rate of 20 ℃/min, preserving the temperature for 5min, cooling the blank along with the furnace to prepare a blank, and carrying out surface grinding and deburring treatment on the prepared blank to obtain the micro-nano polycrystalline diamond composite material.
And grinding and polishing the micro-nano polycrystalline diamond composite material sample after high-pressure sintering, and then carrying out tissue and performance detection, wherein the Vickers hardness value of the obtained sintered block is 127.35 GPa. An X-ray diffraction spectrum of the micro-nano-scale polycrystalline diamond composite material is shown in fig. 3, and a Raman chart of the micro-nano-scale polycrystalline diamond composite material is shown in fig. 4.
Example 7
A preparation method of a micro-nano polycrystalline diamond composite material comprises the following steps:
s1, annealing detonation nano diamond powder with the average grain size of 5nm, wherein the vacuum degree in the annealing treatment is 1Pa, the annealing temperature is 1400 ℃, and the annealing is carried out for 2h to prepare carbon nano shallots with the average grain size of 5 nm;
s2, selecting 7mg of carbon nano-onions, adding 3mg of micron diamond grains, and mixing;
s3, filling a mixture formed by the micron diamond and the carbon nano-onion into a WC hard alloy die for prepressing, wherein the prepressing pressure is 600MPa and the prepressing time is 10S;
and S4, putting the pre-pressed sample into a mould, and sintering at high temperature and high pressure to obtain the micro-nano polycrystalline diamond composite material.
Preferably, the WC cemented carbide die uses laccao in the step S33As heat insulating material, Re as heating body, pyrophyllite as sealing material, MgO or Al2O3As a pressure transmission medium, a W-Re thermocouple measures the temperature.
Preferably, the high-temperature high-pressure sintering process in step S4 is as follows:
firstly, slowly applying pressure to a pre-pressed sample to 18GPa within 17 h; and then, heating the temperature from room temperature to 2100 ℃ at the heating rate of 30 ℃/min, preserving the temperature for 15min, cooling the blank along with the furnace to prepare a blank, and carrying out surface grinding and deburring treatment on the prepared blank to obtain the micro-nano polycrystalline diamond composite material.
And grinding and polishing the micro-nano polycrystalline diamond composite material sample after high-pressure sintering, and then carrying out tissue and performance detection, wherein the Vickers hardness value of the obtained sintered block is 149.35 GPa. An X-ray diffraction spectrum of the micro-nano-scale polycrystalline diamond composite material is shown in fig. 5, and a Raman chart of the micro-nano-scale polycrystalline diamond composite material is shown in fig. 6.
Example 8
A preparation method of a micro-nano polycrystalline diamond composite material comprises the following steps:
s1, annealing detonation nano diamond powder with average grain size of 5nm, wherein the vacuum degree in the annealing treatment is 1.0 × 10-2Pa, the annealing temperature is 1500 ℃, and the temperature is not preserved after annealing, so that the carbon nano-shallot with the average grain size of 5nm is prepared;
s2, selecting 6mg of carbon nano-onions, adding 4mg of micron diamond grains, and mixing;
s3, filling a mixture formed by the micron diamond and the carbon nano-onion into a WC hard alloy die for prepressing, wherein the prepressing pressure is 400MPa and the prepressing pressure is 15S;
and S4, putting the pre-pressed sample into a mould, and sintering at high temperature and high pressure to obtain the micro-nano polycrystalline diamond composite material.
Preferably, the WC cemented carbide die uses laccao in the step S33As heat insulating material, Re as heating body, pyrophyllite as sealing material, MgO or Al2O3As a pressure transmission medium, a W-Re thermocouple measures the temperature.
Preferably, the high-temperature high-pressure sintering process in step S4 is as follows:
firstly, slowly applying pressure to a pre-pressed sample to 20GPa within 19 h; and then, heating the temperature from room temperature to 2150 ℃ at the heating rate of 10 ℃/min, preserving the temperature for 30min, cooling the blank along with the furnace to prepare a blank, and carrying out surface grinding and deburring treatment on the prepared blank to obtain the micro-nano polycrystalline diamond composite material.
And grinding and polishing the micro-nano polycrystalline diamond composite material sample after high-pressure sintering, and then carrying out tissue and performance detection to obtain a sintered block with the Vickers hardness value of 154.26 GPa.
Example 9
A preparation method of a micro-nano polycrystalline diamond composite material comprises the following steps:
s1, annealing detonation nano diamond powder with average grain size of 5nm, wherein vacuum degree in annealing treatmentIs 1.0X 10-1Pa, the annealing temperature is 1600 ℃, and the temperature is kept for 1h after annealing to prepare the carbon nano-shallot with the average grain size of 5 nm;
s2, selecting 5mg of carbon nano-onions, adding 5mg of micron diamond grains, and mixing;
s3, filling a mixture formed by the micron diamond and the carbon nano-onion into a WC hard alloy die for prepressing, wherein the prepressing pressure is 500MPa and the prepressing time is 20S;
and S4, putting the pre-pressed sample into a mould, and sintering at high temperature and high pressure to obtain the micro-nano polycrystalline diamond composite material.
Preferably, the WC cemented carbide die uses laccao in the step S33As heat insulating material, Re as heating body, pyrophyllite as sealing material, MgO or Al2O3As a pressure transmission medium, a W-Re thermocouple measures the temperature.
Preferably, the high-temperature high-pressure sintering process in step S4 is as follows:
firstly, slowly applying pressure to a pre-pressed sample to 22GPa within 21 h; and then, heating the temperature from room temperature to 1600 ℃ at the heating rate of 20 ℃/min, preserving the temperature for 30min, then cooling the blank along with the furnace to prepare a blank, and carrying out surface grinding and deburring treatment on the prepared blank to obtain the micro-nano polycrystalline diamond composite material.
And grinding and polishing the micro-nano polycrystalline diamond composite material sample after high-pressure sintering, and then carrying out tissue and performance detection, wherein the Vickers hardness value of the obtained sintered block is 156.31 GPa.
Example 10
A preparation method of a micro-nano polycrystalline diamond composite material comprises the following steps:
s1, annealing detonation nano diamond powder with average grain size of 5nm, wherein the vacuum degree in the annealing treatment is 1.0 × 10-1Pa, the annealing temperature is 1500 ℃, and the temperature is kept for 2h after annealing to prepare the carbon nano-shallot with the average grain size of 5 nm;
s2, 8mg of carbon nano-onions are selected, 2mg of micron diamond grains are added into the carbon nano-onions, and mixing is carried out;
s3, filling a mixture formed by the micron diamond and the carbon nano-onion into a WC hard alloy die for prepressing, wherein the prepressing pressure is 600MPa and the prepressing time is 25S;
and S4, putting the pre-pressed sample into a mould, and sintering at high temperature and high pressure to obtain the micro-nano polycrystalline diamond composite material.
Preferably, the WC cemented carbide die uses laccao in the step S33As heat insulating material, Re as heating body, pyrophyllite as sealing material, MgO or Al2O3As a pressure transmission medium, a W-Re thermocouple measures the temperature.
Preferably, the high-temperature high-pressure sintering process in step S4 is as follows:
firstly, slowly applying pressure to a pre-pressed sample within 23h to 24 GPa; and then, heating the temperature from room temperature to 1700 ℃ at the heating rate of 30 ℃/min, preserving the temperature for 5min, cooling the blank along with the furnace to prepare a blank, and carrying out surface grinding and deburring treatment on the prepared blank to obtain the micro-nano polycrystalline diamond composite material.
And grinding and polishing the micro-nano polycrystalline diamond composite material sample after high-pressure sintering, and then carrying out tissue and performance detection, wherein the Vickers hardness value of the obtained sintered block is 183.24 GPa.
Example 11
A preparation method of a micro-nano polycrystalline diamond composite material comprises the following steps:
s1, annealing detonation nano diamond powder with the average grain size of 5nm, wherein the vacuum degree is 1Pa, the annealing temperature is 1400 ℃, and the annealing is not carried out to obtain carbon nano shallots with the average grain size of 5 nm;
s2, selecting 7mg of carbon nano-onions, adding 3mg of micron diamond grains, and mixing;
s3, filling a mixture formed by the micron diamond and the carbon nano-onion into a WC hard alloy die for prepressing, wherein the prepressing pressure is 400MPa and the prepressing pressure is 30S;
and S4, putting the pre-pressed sample into a mould, and sintering at high temperature and high pressure to obtain the micro-nano polycrystalline diamond composite material.
Preferably, the WC cemented carbide die uses laccao in the step S33As heat insulating material, Re as heating body, pyrophyllite as sealing material, MgO or Al2O3As a pressure transmission medium, a W-Re thermocouple measures the temperature.
Preferably, the high-temperature high-pressure sintering process in step S4 is as follows:
firstly, slowly applying pressure to a prepressed sample to 25GPa within 24 h; and then heating the mixture from room temperature to 1800 ℃ at the heating rate of 10 ℃/min, preserving the heat for 15min, cooling the mixture along with the furnace to prepare a blank, and grinding and deburring the surface of the prepared blank to obtain the micro-nano polycrystalline diamond composite material.
And grinding and polishing the micro-nano polycrystalline diamond composite material sample after high-pressure sintering, and then carrying out tissue and performance detection, wherein the Vickers hardness value of the obtained sintered block is 192.43 GPa.
Example 12
A preparation method of a micro-nano polycrystalline diamond composite material comprises the following steps:
s1, annealing detonation nano diamond powder with average grain size of 5nm, wherein the vacuum degree in the annealing treatment is 1.0 × 10-2Pa, the annealing temperature is 1600 ℃, and the annealing is not carried out to obtain the carbon nano-shallot with the average grain size of 5 nm;
s2, selecting 7mg of carbon nano-onions, adding 3mg of micron diamond grains, and mixing;
s3, filling a mixture formed by the micron diamond and the carbon nano-onion into a WC hard alloy die for prepressing, wherein the prepressing pressure is 400MPa and the prepressing pressure is 30S;
and S4, putting the pre-pressed sample into a mould, and sintering at high temperature and high pressure to obtain the micro-nano polycrystalline diamond composite material.
Preferably, the WC cemented carbide die uses laccao in the step S33As heat insulating material, Re as heating body, pyrophyllite as sealing material, MgO or Al2O3As a pressure transmission medium, a W-Re thermocouple measures the temperature.
Preferably, the high-temperature high-pressure sintering process in step S4 is as follows:
firstly, slowly applying pressure to a prepressed sample to 25GPa within 24 h; and then heating the mixture from room temperature to 2150 ℃ at the heating rate of 10 ℃/min, preserving the heat for 60min, cooling the mixture along with the furnace to prepare a blank, and grinding and deburring the surface of the prepared blank to obtain the micro-nano polycrystalline diamond composite material.
And grinding and polishing the micro-nano polycrystalline diamond composite material sample after high-pressure sintering, and then carrying out tissue and performance detection to obtain a sintered block with the Vickers hardness value of 200 GPa.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (6)

1. A micro-nano polycrystalline diamond composite characterized by: the components comprise carbon nano-shallot and micro-diamond;
the mass percent of the micro diamond is 20-50 wt.%, and the balance is carbon nano shallot.
2. The micro-nano scale polycrystalline diamond composite according to claim 1, wherein: the average particle size of the carbon nano shallots is 5 nm;
the micron diamond is a crushed material, the granularity of the micron diamond is 0.5-5 microns, and the purity of the micron diamond is 99%.
3. The micro-nano scale polycrystalline diamond composite according to claim 1, wherein: the micro-nano polycrystalline diamond composite material has the Vickers hardness of 30-200 GPa.
4. A method of preparing a micro-nano polycrystalline diamond composite material according to any one of claims 1 to 3, comprising the steps of:
s1, annealing detonation nano diamond powder with average grain size of 5nm, wherein the vacuum degree in the annealing treatment is 1-1.0 multiplied by 10-2Pa, annealing temperature of 900-1600 ℃, and keeping the temperature for 0-2 h after annealing to prepare the carbon nano-shallot with the average grain size of 5 nm;
s2, adding micron diamond grains into the carbon nano shallot prepared in the step S1, and mixing, wherein the mass percent of the micron diamond grains is 20-50 wt%;
s3, filling a mixture formed by the micron diamond and the carbon nano-onion into a WC hard alloy die for prepressing, wherein the prepressing pressure is 400-600 MPa and the prepressing pressure is 10-30S;
and S4, putting the pre-pressed sample into a mould, and sintering at high temperature and high pressure to obtain the micro-nano polycrystalline diamond composite material.
5. The method of preparing a micro-nano polycrystalline diamond composite according to claim 3, wherein: the WC cemented carbide mold in the step S3 uses LaCaO3As heat insulating material, Re as heating body, pyrophyllite as sealing material, MgO or Al2O3As a pressure transmission medium, a W-Re thermocouple measures the temperature.
6. The method of preparing a micro-nano polycrystalline diamond composite according to claim 3, wherein:
the high-temperature high-pressure sintering process in the step S4 includes:
firstly, slowly applying pressure to a pre-pressed sample within 10-24h to 8-25 GPa; and then, heating the temperature to 1600-2150 ℃ from room temperature at a heating rate of 10-30 ℃/min, preserving the temperature for 5-60 min, cooling the temperature along with the furnace to obtain a blank, and carrying out surface grinding and deburring treatment on the prepared blank to obtain the micro-nano polycrystalline diamond composite material.
CN201911354946.7A 2019-12-25 2019-12-25 Micro-nano polycrystalline diamond composite material and preparation method thereof Pending CN111056842A (en)

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