CN110552012B - Method for cleaning hard alloy substrate for superhard composite material - Google Patents
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Abstract
The invention discloses a method for cleaning a hard alloy substrate for a superhard composite material, which comprises the following cleaning processes: 1) alkalization treatment; 2) acidizing; 3) activating treatment; 4) high vacuum purification treatment; 5) and (5) performing ion bombardment purification treatment. The method can effectively remove impurities adsorbed on the surface of the hard alloy matrix, so that the hard alloy matrix has high cleanliness, the surface activity and the outward bonding reaction capacity of the hard alloy matrix are improved, the bonding strength between the superhard material and the hard alloy matrix is improved, and the phenomena of falling off and damage of the superhard composite material are avoided.
Description
Technical Field
The invention belongs to the field of superhard materials and hard alloy composite materials, and particularly relates to a method for cleaning a hard alloy substrate for a superhard composite material.
Background
The superhard composite material is formed by sintering a superhard material and a hard alloy matrix under the condition of high temperature and high pressure, and is an excellent composite material because the superhard material has the characteristics of high hardness and good wear resistance, and simultaneously has the characteristics of strong shock resistance and good weldability of the hard alloy, and the superhard composite material is widely applied to the aspects of machining tools, drilling teeth for petroleum/geological drilling, wire drawing dies and the like.
In the ultra-high pressure and high temperature sintering of the ultra-hard composite material, the sintering quality of the ultra-hard composite material is directly influenced due to the surface cleanliness of the hard alloy substrate. Therefore, before sintering, the cemented carbide substrate is strictly treated to remove moisture, oxides, foreign atoms and the like on the surface of the substrate, otherwise, excessive impurities can affect the interface combination of the superhard material and the cemented carbide substrate, and the superhard material is delaminated and cracked and damaged. At present, the hard alloy matrix treated in the prior art has poor surface cleanliness and activity, so that the improvement of the bonding strength between the superhard material and the hard alloy matrix is influenced.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for cleaning a hard alloy matrix for a superhard composite material, which can effectively remove impurities adsorbed on the surface of the hard alloy matrix, ensure that the hard alloy matrix has high purity, increase the activity and the outward bonding reaction capacity of the surface of the hard alloy matrix and improve the bonding strength between the superhard material and the hard alloy matrix.
The invention adopts the following technical scheme:
a cleaning method of a hard alloy substrate for a superhard composite material comprises the following steps:
1) alkalization treatment: soaking the hard alloy substrate into a low-alkali solution, boiling for 2-5 min, washing with deionized water to be neutral, soaking into a high-alkali solution, washing for 15-20 min in a shaking manner, taking out the hard alloy substrate, and washing with ionized water to be neutral;
2) acidifying: immersing a hard alloy substrate into a dilute sulfuric acid solution, washing for 2-5 min by ultrasonic oscillation, washing to be neutral by deionized water, immersing into the dilute hydrochloric acid solution, washing for 2-5 min by ultrasonic oscillation, and washing to be neutral by the deionized water;
3) activation treatment: soaking a hard alloy substrate into a mixed solution of palladium oxide and hydrochloric acid, carrying out magnetic stirring treatment for 3-8 min, washing the hard alloy substrate to be neutral by using deionized water, then sequentially placing the hard alloy substrate into absolute ethyl alcohol and acetone, respectively carrying out ultrasonic oscillation cleaning for 5-10 min and 10-15 min, and then drying the hard alloy substrate by using nitrogen;
the mixed solution of palladium oxide and hydrochloric acid takes deionized water as a solvent, the concentration of the palladium oxide in the mixed solution of palladium oxide and hydrochloric acid is 0.8-1.2g/L, the addition amount of the hydrochloric acid with the mass fraction of 40% is 180-220mL/L, namely 180-220mL of hydrochloric acid is added into each 1L of the mixed solution;
the palladium oxide and the hydrochloric acid are of analytical pure grade;
4) high vacuum purification treatment: placing the hard alloy matrix in a vacuum sintering furnace, vacuumizing, heating and reducing;
5) ion bombardment purification treatment:
the conditions were as follows: vacuumizing to the indoor air pressure of 5 × 10-3Filling argon under Pa until the indoor air pressure is 15-20 Pa, then controlling the working voltage between 1200-1500V, and carrying out ion bombardment purification for 5-10 min;
the ion bombardment purification treatment can be realized by adopting a surface treatment device in the prior art, such as a diamond surface treatment device;
further, in the step 1), the low alkali solution is prepared by mixing deionized water and sodium hydroxide in a mass ratio of 1: 0.1-0.2;
the high alkali solution is prepared from KOH and K3Fe(CN) 6And H2O is mixed according to the mass ratio of 1: 0.8-1.2: 8-12, the sodium hydroxide, KOH and K3Fe(CN)6For analytical grade.
Further, in the step 2), the dilute sulfuric acid solution is prepared by mixing 98% by mass of sulfuric acid and deionized water in a volume ratio of 1: 4-5, mixing;
the dilute hydrochloric acid solution is prepared from 40% hydrochloric acid and deionized water in a volume ratio of 1: 1-1.2 mixing;
the sulfuric acid and hydrochloric acid are analytical grade.
Further, in the step 1), the ultrasonic oscillation cleaning power is 40-60W; in the step 2) and the step 3), the ultrasonic oscillation cleaning power is 50-70W.
Further, in the step 3), the acetone and the absolute ethyl alcohol are of analytical pure grade, and the conductivity value of the deionized water is less than 2 muS/cm.
Further, in the step 4), the vacuum-pumping, heating and reducing treatment comprises the following specific steps: placing the hard alloy matrix in a vacuum sintering furnace, and rough vacuumizing until the air pressure in the furnace reaches 10 multiplied by 10-2Heating to 250-300 ℃ below Pa, preserving heat for 20-30 min, and then continuously vacuumizing until the air pressure in the furnace is 4 multiplied by 10-3Keeping the temperature below Pa at 400-500 ℃ for 2-3 min, stopping vacuumizing, filling reducing gas into the vacuum heating furnace until the pressure in the furnace is 15-25 Mbar, and carrying out reduction treatment on the gas by 0.5-E1h, vacuumizing until the air pressure in the furnace is 5 multiplied by 10-4Raising the temperature to 600-700 ℃ below Pa, preserving the heat for 0.5-1 h, and finally vacuumizing until the air pressure in the furnace is 8 multiplied by 10-5Pa below, and keeping the temperature of 600-700 ℃ for 0.2-0.5 h.
Further, in the step 4), the reducing gas is one or two of hydrogen, carbon monoxide and ammonia gas, the purity of the charged hydrogen gas is more than 99.99999%, and the purity of the charged carbon monoxide and ammonia gas is more than 99.999%.
Further, in the step 5), the inert gas is one or two of argon, helium and krypton, and the purity of the argon, helium and krypton is more than 99.999%.
In order to improve the cleaning effect and avoid introducing new impurities, the reagents used in the method are all analytical pure grades.
Compared with the prior art, the invention has the following advantages:
in the invention, the surface of the hard alloy matrix is sequentially subjected to alkalization, acidification, activation, high vacuum purification treatment and ion bombardment purification treatment to obtain the hard alloy matrix with high cleanliness and high surface activity, and the method has the beneficial effects that:
(1) the alkalization treatment is mainly used for removing oil stains, non-metallic impurities and the like adsorbed on the surface of the hard alloy substrate; the acidification treatment mainly removes impurities such as metal oxides on the surface of the hard alloy matrix.
(2) The surface of the hard alloy matrix is fully activated through the activation treatment of the mixed solution of palladium oxide and hydrochloric acid, the surface activity of the hard alloy is increased, and the combination of the hard alloy matrix and the superhard material and the improvement of the comprehensive performance are facilitated.
(3) Before high vacuum heating treatment, the dangling bonds on the surface of the hard alloy matrix adsorb a great amount of hetero atoms, the hard alloy matrix is kept in a high vacuum state for heat treatment, and under a negative pressure state, impurities (hetero atoms) such as gas adsorbed on the surface of the hard alloy matrix are quickly desorbed from the surface of the matrix and pumped out due to the fact that the desorption speed is higher than the adsorption speed, the surface of the matrix is purified and activated, and the impurities can easily generate chemical action, so that the bonding strength of the superhard composite material is improved.
(4) The invention can effectively eliminate the stripping of gas particles or oxide films adsorbed on the surface of the hard alloy matrix through positive ion bombardment purification treatment, and has high cleanliness.
Drawings
Fig. 1 is a fracture SEM of the polycrystalline diamond layer of the sample of example 1;
fig. 2 is a fracture SEM of the polycrystalline diamond layer of the sample of example 2;
fig. 3 is a fracture SEM of the polycrystalline diamond layer of the sample of example 3;
FIG. 4 is an ultrasonic flaw detection chart of a sample interface in example 1;
FIG. 5 is an ultrasonic flaw detection chart of a sample interface in example 1;
FIG. 6 is an ultrasonic flaw detection chart of a sample interface in example 1;
FIG. 7 is an ultrasonic flaw detection chart of the sample interface in the comparative example.
Detailed Description
The present invention will be described in further detail with reference to preferred examples, but the scope of the present invention is not limited thereto.
In the following examples, the reagents used were of analytical grade, and the conductivity value of the deionized water used was less than 2 μ S/cm.
Example 1 YG12X cemented carbide substrate surface cleaning treatment
1) Alkalization treatment: soaking the hard alloy matrix in a low alkali solution for boiling for 2min, washing the hard alloy matrix to be neutral by using deionized water, then soaking the hard alloy matrix in a high alkali solution for ultrasonic oscillation and cleaning for 15min, and then taking out the hard alloy matrix and washing the hard alloy matrix to be neutral by using the deionized water;
in this embodiment, the weak base solution is prepared from deionized water and sodium hydroxide in a mass ratio of 1: 0.1 is mixed; the strong alkaline solution is prepared from KOH and K3Fe(CN)6And H2O is mixed according to the mass ratio of 1: 0.8: 8, the sodium hydroxide, the KOH and the K are mixed according to the proportion3Fe(CN)6For analytical grade; the ultrasonic oscillation cleaning power is 40W;
2) acidifying: immersing the hard alloy substrate into a dilute sulfuric acid solution, ultrasonically vibrating and cleaning for 2min, washing the substrate to be neutral by using deionized water, immersing the substrate into a dilute hydrochloric acid solution, ultrasonically vibrating and cleaning for 2min, and washing the substrate to be neutral by using the deionized water;
in this embodiment, the dilute sulfuric acid solution is prepared by mixing 98% by mass of sulfuric acid and deionized water in a volume ratio of 1: 4, mixing; the dilute hydrochloric acid solution is prepared from 40% hydrochloric acid and deionized water in a volume ratio of 1: 1, mixing; the sulfuric acid and the hydrochloric acid are of analytical pure grade; the ultrasonic oscillation cleaning power is 50W;
3) activation treatment: soaking a hard alloy substrate into a mixed solution of palladium oxide (0.8 g/L) and hydrochloric acid (180 ml/L) for magnetic stirring treatment for 3min, washing the hard alloy substrate to be neutral by using deionized water, then sequentially placing the hard alloy substrate in absolute ethyl alcohol and acetone for ultrasonic oscillation cleaning for 5min and 10min, and then drying the hard alloy substrate by using nitrogen; the mixed solution takes deionized water as a solvent, the concentration of palladium oxide is 0.8g/L, the addition amount of hydrochloric acid with the mass fraction of 40% is 180mL/L, namely 180mL of hydrochloric acid is added into every 1L of the mixed solution; the palladium oxide and the hydrochloric acid are of analytical pure grade; the acetone and the absolute ethyl alcohol are analytical pure grades;
4) high vacuum purification treatment: placing the hard alloy matrix in a vacuum sintering furnace, firstly vacuumizing until the air pressure in the furnace reaches 10 multiplied by 10-2Heating to 250 deg.C below Pa, maintaining for 20min, and continuously vacuumizing until the pressure in the furnace is 4 × 10-3Heating to 400 deg.C below Pa for 2min, stopping vacuumizing, introducing hydrogen gas into the vacuum heating furnace until the pressure in the furnace is 15Mbar, reducing the matrix for 0.5 hr, and vacuumizing until the pressure in the furnace is 5 × 10-4Heating to 600 deg.C below Pa, maintaining for 0.5 hr, and vacuumizing to 8 × 10-5Pa below, keeping the temperature at 600 ℃ for 0.2 h; the purity of the hydrogen filled in is more than 99.99999%.
5) And (3) positive ion bombardment purification treatment: placing the hard alloy substrate on a cathode tray of a diamond surface treatment device, connecting the tray serving as a cathode with a power supply on a circuit, covering a bell jar for sealing, and vacuumizing to indoor air pressure of 5 × 10 by a pipeline-3Below Pa, the air pressure is 15Pa through the pipeline 10And then controlling the working voltage to be 1200-1300V, and carrying out ion bombardment purification for 5min to complete the cleaning operation.
Diamond micropowder with a particle size of 10 μm and YG12X cemented carbide substrate treated in example 1 were used as raw materials, a composite was assembled by reversing two refractory metal cups, and the composite was placed in an assembly block of a composite block and synthesized by a cubic press at 1500 ℃ and 5.8GPa for 15 min. After sintering, the sample is subjected to external grinding, flat grinding, grinding and polishing, and the final size is 25mm in diameter, 3.0mm in total thickness and 0.5mm in polycrystalline diamond layer.
A. Scanning electron microscopy of sample interfaces
The binding state of the sample interface was examined by JSM-7610F scanning electron microscopy.
Fig. 1 is a SEM photograph of a fracture of a sample diamond layer, wherein the black area is the diamond layer and the left silvery white area is the cemented carbide substrate, as can be seen from fig. 1: the interface bond between the diamond layer and the cemented carbide substrate was intact and no seams were observed.
B. Ultrasonic inspection of sample interfaces
And (3) checking whether the sample interface has defects such as cracks, delamination and the like through an American SONIX ultrasonic scanning microscope.
Fig. 4 is a sonogram of the sample interface, from which it can be seen that: the interface between the diamond layer and the hard alloy matrix is well combined, and the defects of cracks, delamination, air holes, inclusions and the like are avoided.
C. Shear strength testing of sample interfaces
The shear strength test is carried out on a self-made shear test mould by adopting the method introduced in the literature ' composition, structure and performance (J) ' of phi 25mm PDC composite material, 2001, 16 (5):915-920 ', the shear test is carried out under the same pressure (196N), and the interface bonding (shear) strength of a test sample is 3.6GPa, which shows that the strength between a diamond layer and a hard alloy matrix is higher.
Example 2 YG12X cemented carbide substrate surface cleaning treatment
1) Alkalization treatment: soaking the hard alloy matrix into a low-alkali solution to boil for 3.5min, washing the hard alloy matrix to be neutral by using deionized water, then soaking the hard alloy matrix into a high-alkali solution to perform ultrasonic oscillation cleaning for 15-20 min, and then taking out the hard alloy matrix and washing the hard alloy matrix to be neutral by using the deionized water;
in this example, the low alkali solution is prepared by mixing deionized water and sodium hydroxide in a mass ratio of 1: 0.15 is mixed;
the high alkali solution is prepared from KOH and K3Fe(CN)6And H2O is mixed according to the mass ratio of 1: 1: 10 in proportion;
the sodium hydroxide, KOH and K3Fe(CN)6For analytical grade; the ultrasonic oscillation cleaning power is 50W;
2) acidifying: immersing the hard alloy substrate into a dilute sulfuric acid solution, ultrasonically vibrating and cleaning for 3.5min, washing the substrate to be neutral by using deionized water, immersing the substrate into a dilute hydrochloric acid solution, ultrasonically vibrating and cleaning for 3.5min, and washing the substrate to be neutral by using the deionized water;
in this embodiment, the dilute sulfuric acid solution is prepared by mixing 98% by mass of sulfuric acid and deionized water in a volume ratio of 1: 4.5 mixing; the dilute hydrochloric acid solution is prepared from 40% hydrochloric acid and deionized water in a volume ratio of 1: 1.1 mixing;
the sulfuric acid and the hydrochloric acid are of analytical pure grade; the ultrasonic oscillation cleaning power is 60W.
3) Activation treatment: soaking the hard alloy substrate into a mixed solution of palladium oxide and hydrochloric acid, carrying out magnetic stirring treatment for 5.5 min, washing the hard alloy substrate to be neutral by using deionized water, then sequentially placing the hard alloy substrate into absolute ethyl alcohol and acetone, respectively carrying out ultrasonic oscillation cleaning for 7.5 min and 12 min, and then blowing the hard alloy substrate by using nitrogen;
the mixed solution takes deionized water as a solvent, the concentration of palladium oxide is 1.0g/L, the addition amount of hydrochloric acid with the mass fraction of 40% is 200mL/L, namely 200mL of hydrochloric acid is added into every 1L of the mixed solution;
the palladium oxide and the hydrochloric acid are of analytical pure grade; the acetone and the absolute ethyl alcohol are analytical pure grades.
4) High vacuum purification treatment: roughly vacuumizing the furnace until the pressure in the furnace reaches 10 multiplied by 10-2Heating to 275 deg.C below PaKeeping the temperature for 25min, and then continuously vacuumizing until the air pressure in the furnace is 4 multiplied by 10-3Heating to 450 deg.C below Pa, keeping the temperature for 1.5min, stopping vacuumizing, introducing carbon monoxide with an internal pressure of 20Mbar into a vacuum heating furnace to reduce the matrix for 0.75 hr, and vacuumizing to an internal pressure of 5 × 10-4Raising the temperature to 650 ℃ below Pa, keeping the temperature for 0.75h, and then vacuumizing until the air pressure in the furnace is 8 x 10-5Pa below, at 650 deg.C for 0.35 h. (ii) a The purity of the charged carbon monoxide is more than 99.999 percent.
5) And (3) positive ion bombardment purification treatment: the hard alloy matrix is placed on a cathode tray of the diamond surface treatment device, and the tray is used as a cathode and is communicated with a power supply on a circuit. After the bell jar is covered and sealed, the air pressure in the room is pumped to 5 multiplied by 10 through the pipeline-3And (4) below Pa, feeding helium with the air pressure of 17 Pa in the chamber through a pipeline, controlling the working voltage between 1300 and 1400V, and performing ion bombardment purification for 7 min to finish the cleaning operation.
Diamond micropowder with a particle size of 10 μm and YG12X cemented carbide substrate treated in example 2 were used as raw materials, and a composite was assembled by reversing two refractory metal cups, and the composite was placed in an assembly block of a composite block, and synthesized by a cubic press at 1500 ℃ and 5.8GPa for 15 min. After sintering, the sample is subjected to external grinding, flat grinding, grinding and polishing, and the final size is 25mm in diameter, 3.0mm in total thickness and 0.5mm in polycrystalline diamond layer.
A. Scanning electron microscopy of sample interfaces
The binding state of the sample interface was examined by JSM-7610F scanning electron microscopy.
Fig. 2 is a fracture SEM photograph of the sample diamond layer, where the black area is the diamond layer and the left silvery white area is the cemented carbide substrate. As can be seen from fig. 2: the interface bond between the diamond layer and the cemented carbide substrate was intact and no seams were observed.
B. Ultrasonic inspection of sample interfaces
And (3) checking whether the sample interface has defects such as cracks, delamination and the like through an American SONIX ultrasonic scanning microscope.
Fig. 5 is a sonogram of the sample interface, from which it can be seen that: the interface between the diamond layer and the hard alloy matrix is well combined, and the defects of cracks, delamination, air holes, inclusions and the like are avoided.
C. Shear strength testing of sample interfaces
The shear strength test is carried out on a self-made shear test mould by adopting the method introduced in the literature ' composition, structure and performance (J) ' of phi 25mm PDC composite material, 2001, 16 (5):915-920 ', the shear test is carried out under the same pressure (196N), and the interface bonding (shear) strength of the test sample is 3.55GPa, which shows that the bonding strength between the polycrystalline diamond layer and the hard alloy matrix of the sample is higher.
Example 3 YG13X cemented carbide substrate surface cleaning treatment
1) Alkalization treatment: soaking the hard alloy matrix in a low alkali solution for boiling for 5min, washing the hard alloy matrix to be neutral by using deionized water, then soaking the hard alloy matrix in a high alkali solution for ultrasonic oscillation and cleaning for 20min, and then taking out the hard alloy matrix and washing the hard alloy matrix to be neutral by using the deionized water;
the low-alkali solution is prepared from deionized water and sodium hydroxide in a mass ratio of 1: 0.2 is mixed; the high alkali solution is prepared from KOH and K3Fe(CN)6And H2O is mixed according to the mass ratio of 1: 1.2: 12, the sodium hydroxide, KOH and K3Fe(CN)6For analytical grade; the ultrasonic oscillation cleaning power is 60W;
2) acidifying: immersing the hard alloy substrate into a dilute sulfuric acid solution, ultrasonically vibrating and cleaning for 5min, washing the substrate to be neutral by using deionized water, immersing the substrate into a dilute hydrochloric acid solution, ultrasonically vibrating and cleaning for 5min, and washing the substrate to be neutral by using the deionized water;
the dilute sulfuric acid solution is prepared by mixing 98% sulfuric acid and deionized water in a volume ratio of 1: 5, mixing the components;
the dilute hydrochloric acid solution is prepared from 40% hydrochloric acid and deionized water in a volume ratio of 1: 1.2 mixing;
the sulfuric acid and the hydrochloric acid are of analytical pure grade; the ultrasonic oscillation cleaning power is 70W.
3) Activation treatment: soaking the hard alloy substrate into a mixed solution of palladium oxide and hydrochloric acid, carrying out magnetic stirring treatment for 8 min, washing the hard alloy substrate to be neutral by using deionized water, then sequentially placing the hard alloy substrate in absolute ethyl alcohol and acetone, carrying out ultrasonic oscillation cleaning for 10min and 15min, and then drying the hard alloy substrate by using nitrogen;
the mixed solution takes deionized water as a solvent, the concentration of palladium oxide is 1.2g/L, the addition amount of hydrochloric acid with the mass fraction of 40% is 220mL/L, namely 220mL of hydrochloric acid is added into every 1L of the mixed solution; the palladium oxide and the hydrochloric acid are of analytical pure grade; the acetone and the absolute ethyl alcohol are analytical pure grades.
4) High vacuum purification treatment: placing the hard alloy matrix in a vacuum sintering furnace, firstly vacuumizing until the air pressure in the furnace reaches 10 multiplied by 10-2Heating to 300 deg.C below Pa, maintaining the temperature for 30min, and further vacuumizing to 4 × 10-3Heating to 500 deg.C below Pa for 3min, stopping vacuumizing, introducing ammonia gas into the vacuum heating furnace until the pressure in the furnace is 25Mbar, reducing the matrix for 1 hr, and vacuumizing until the pressure in the furnace is 5 × 10-4Heating to 700 deg.C below Pa, maintaining for 1 hr, and vacuumizing to 8 × 10-5Pa below, keeping the temperature at 700 ℃ for 0.5 h; the purity of the charged ammonia gas is more than 99.999 percent.
5) And (3) positive ion bombardment purification treatment: placing the hard alloy substrate on a cathode tray of a diamond surface treatment device, connecting the tray serving as a cathode with a power supply on a circuit, covering a bell jar for sealing, and vacuumizing to indoor air pressure of 5 × 10 by a pipeline-3And (3) feeding the krypton gas with the air pressure of 20Pa in the chamber through a pipeline under Pa, and then controlling the working voltage to be 1400-1500V to perform ion bombardment purification for 10 min.
Diamond micropowder with a particle size of 10 μm and YG13X cemented carbide substrate treated in example 2 were used as raw materials, and the composite was assembled by reversing two refractory metal cups, and placed in a composite block, and synthesized by a cubic press at 1500 ℃ and 5.8GPa for 15 min. After sintering, the sample is subjected to external grinding, flat grinding, grinding and polishing, and the final size is 25mm in diameter, 3.0mm in total thickness and 0.5mm in polycrystalline diamond layer.
A. Scanning electron microscopy of sample interfaces
The binding state of the sample interface was examined by JSM-7610F scanning electron microscopy.
Fig. 3 is a fracture SEM photograph of the sample diamond layer, where the black area is the diamond layer and the left silvery-white area is the cemented carbide substrate. As can be seen from fig. 3: the interface bond between the diamond layer and the cemented carbide substrate was intact and no seams were observed.
B. Ultrasonic inspection of sample interfaces
And (3) checking whether the sample interface has defects such as cracks, delamination and the like through an American SONIX ultrasonic scanning microscope.
FIG. 6 is a sonogram of a sample interface, from which it can be seen that: the interface between the diamond layer and the hard alloy matrix of the sample is well combined, and the defects of cracks, delamination, air holes, inclusions and the like are avoided.
C. Shear strength testing of sample interfaces
The shear strength test is carried out on a self-made shear test mould by adopting the method introduced in the literature ' composition, structure and performance (J) ' of phi 25mm PDC composite material, 2001, 16 (5):915-920 ', the shear test is carried out under the same pressure (196N), and the interface bonding (shear) strength of the test sample is 3.58GPa, which shows that the bonding strength between the polycrystalline diamond layer and the hard alloy matrix of the sample is higher.
Comparative example YG12 base alloy cleaned by prior art
The cleaning treatment method in the prior art comprises the following steps: the YG12 hard alloy matrix was placed in an acetone solution for 5min of ultrasonic cleaning and then placed in a vacuum oven for 10min at 100 ℃.
Diamond micropowder with the particle size of 10 mu m and YG12 hard alloy matrix processed by test example are used as raw materials, a composite body is assembled in a mode that two high-temperature resistant metal cups are reversely buckled, and the composite body is placed in a composite block assembly and is synthesized for 25min by a cubic press under the conditions that the temperature is 1500 ℃ and the pressure is 5.8 GPa. After sintering, the sample is subjected to external grinding, flat grinding, grinding and polishing, and the final size is 25mm in diameter, 3.0mm in total thickness and 0.5mm in polycrystalline diamond layer.
A. Ultrasonic inspection of sample interfaces
And (3) checking whether the sample interface has defects such as cracks, delamination and the like through an American SONIX ultrasonic scanning microscope.
Fig. 7 is a sonogram of the sample interface, from which it can be seen that: the interface between the polycrystalline diamond layer of the prior art cleaned YG12X cemented carbide substrate and the cemented carbide substrate exhibited delamination cracking defects (the delamination cracking regions were black edge portions).
B. Shear strength testing of sample interfaces
The method described in the document "composition, structure and performance (J) of 25mm PDC composite material, academic report on inorganic materials, 2001, 16 (5): 915-920" is adopted to carry out a shear strength test on a self-made shear test die, a shear test is carried out under the same pressure (196N), and the interface bonding (shear) strength of a tested sample is 2.3GPa, which shows that the bonding strength between the polycrystalline diamond layer and the hard alloy matrix of the YG12X hard alloy processed in the prior art is poor.
Finally, it should be noted that: the above embodiments are merely illustrative and not restrictive of the technical solutions of the present invention, and any equivalent substitutions and modifications or partial substitutions made without departing from the spirit and scope of the present invention should be included in the scope of the claims of the present invention.
Claims (4)
1. A method for cleaning a hard alloy substrate for a superhard composite material is characterized by sequentially carrying out the following steps:
1) alkalization treatment: soaking the hard alloy substrate into a low alkali solution, boiling for 2-5 min, washing with deionized water to be neutral, then soaking the hard alloy substrate into a high alkali solution, washing for 15-20 min in a vibration manner, taking out the hard alloy substrate, and washing with deionized water to be neutral;
2) acidifying: immersing the hard alloy substrate into a dilute sulfuric acid solution, ultrasonically vibrating and cleaning for 2-5 min, washing with deionized water to be neutral, immersing into a dilute hydrochloric acid solution, ultrasonically vibrating and cleaning for 2-5 min, and washing with deionized water to be neutral;
3) activation treatment: soaking the hard alloy substrate into a mixed solution of palladium oxide and hydrochloric acid, stirring for 3-8 min, washing with deionized water to be neutral, then sequentially placing the hard alloy substrate into absolute ethyl alcohol and acetone, respectively carrying out ultrasonic oscillation cleaning for 5-10 min and 10-15 min, and then carrying out nitrogen blow-drying; wherein the mixed solution of palladium oxide and hydrochloric acid takes deionized water as a solvent, the concentration of the palladium oxide in the mixed solution of palladium oxide and hydrochloric acid is 0.8-1.2g/L, and the addition amount of the hydrochloric acid with the mass fraction of 40% is 180-220 ml/L;
4) high vacuum purification treatment: placing the hard alloy matrix in a vacuum sintering furnace, vacuumizing, heating and reducing;
5) ion bombardment purification treatment: the conditions for ion bombardment purification treatment of the hard alloy matrix are as follows: vacuumizing to the indoor air pressure of 5 × 10-3Filling argon under Pa until the indoor air pressure is 15-20 Pa, then controlling the working voltage between 1200-1500V, and carrying out ion bombardment purification for 5-10 min;
in the step 4), the vacuum-pumping, heating and reducing treatment comprises the following specific steps: placing the hard alloy matrix in a vacuum sintering furnace, firstly vacuumizing until the air pressure in the furnace reaches 10 multiplied by 10-2Heating to 250-300 ℃ below Pa, preserving heat for 20-30 min, and then continuously vacuumizing until the air pressure in the furnace is 4 multiplied by 10-3Raising the temperature to 400-500 ℃ below Pa, keeping the temperature for 2-3 min, stopping vacuumizing, filling reducing gas into the vacuum sintering furnace until the pressure in the furnace is 15-25 Mbar, reducing for 0.5-1 h, and vacuumizing until the pressure in the furnace is 5 multiplied by 10-4Raising the temperature to 600-700 ℃ below Pa, preserving the heat for 0.5-1 h, and finally vacuumizing until the air pressure in the furnace is 8 multiplied by 10-5Keeping the temperature below Pa for 0.2-0.5 h at 600-700 ℃;
in the step 1), the low alkali solution is prepared by mixing deionized water and NaOH in a mass ratio of 1: 0.1-0.2;
in step 1), the high alkali solution is prepared from KOH and K3Fe(CN)6And deionized water in a mass ratio of 1: 0.8-1.2: 8-12 in proportion;
in the step 2), the dilute sulfuric acid solution is prepared by mixing 98% by mass of sulfuric acid and deionized water in a volume ratio of 1: 4-5, mixing;
in the step 2), the dilute hydrochloric acid solution is prepared by mixing 40% by mass of hydrochloric acid and deionized water in a volume ratio of 1: 1 to 1.2.
2. The method of cleaning a cemented carbide substrate for superhard composites as claimed in claim 1, wherein the NaOH is analytical grade, the KOH and K being3Fe(CN)6For analytical purification, the sulfuric acid is analytical purification grade, and the hydrochloric acid is analytical purification grade.
3. The method of cleaning a cemented carbide substrate for superhard composite material according to any one of claims 1 to 2, wherein the conductivity value of the deionized water is less than 2 μ S/cm.
4. The method of cleaning a cemented carbide substrate for superhard composite material according to claim 1, wherein the reducing gas is one or two of hydrogen, carbon monoxide and ammonia, the purity of the hydrogen is 99.99999% or more, and the purity of the carbon monoxide and ammonia is 99.999% or more.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018139A (en) * | 2014-06-20 | 2014-09-03 | 哈尔滨工业大学 | Hollow microsphere/Ni-Fe-P/Cu composite coating and preparation method thereof |
| CN104962793A (en) * | 2015-06-23 | 2015-10-07 | 中南钻石有限公司 | Polycrystalline diamond compact with excellent electric conductivity and method for manufacturing polycrystalline diamond compact |
| CN106316403A (en) * | 2016-08-18 | 2017-01-11 | 中南钻石有限公司 | Fine-grained cubic boron nitride blade and preparation method thereof |
| CN106637157A (en) * | 2017-01-04 | 2017-05-10 | 郑州中南杰特超硬材料有限公司 | Method for plating nickel on surface of super-hard material |
| CN107363257A (en) * | 2017-07-24 | 2017-11-21 | 中南钻石有限公司 | A kind of polycrystalline diamond blank vacuum purification method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104018139A (en) * | 2014-06-20 | 2014-09-03 | 哈尔滨工业大学 | Hollow microsphere/Ni-Fe-P/Cu composite coating and preparation method thereof |
| CN104962793A (en) * | 2015-06-23 | 2015-10-07 | 中南钻石有限公司 | Polycrystalline diamond compact with excellent electric conductivity and method for manufacturing polycrystalline diamond compact |
| CN106316403A (en) * | 2016-08-18 | 2017-01-11 | 中南钻石有限公司 | Fine-grained cubic boron nitride blade and preparation method thereof |
| CN106637157A (en) * | 2017-01-04 | 2017-05-10 | 郑州中南杰特超硬材料有限公司 | Method for plating nickel on surface of super-hard material |
| CN107363257A (en) * | 2017-07-24 | 2017-11-21 | 中南钻石有限公司 | A kind of polycrystalline diamond blank vacuum purification method |
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