CN109402475B - Heat treatment method for diamond composite material blank - Google Patents
Heat treatment method for diamond composite material blank Download PDFInfo
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- CN109402475B CN109402475B CN201811330899.8A CN201811330899A CN109402475B CN 109402475 B CN109402475 B CN 109402475B CN 201811330899 A CN201811330899 A CN 201811330899A CN 109402475 B CN109402475 B CN 109402475B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
- B22F2007/042—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal characterised by the layer forming method
Abstract
The invention discloses a heat treatment method of a diamond composite material blank, which sequentially comprises the following steps: step one, placing an assembled diamond composite material blank into a vacuum furnace, heating to a first temperature under a vacuum condition, and then preserving heat for a certain time; step two, continuously heating the blank obtained in the step one to a second temperature under a vacuum condition, preserving heat for a certain time, and intermittently filling hydrogen into the vacuum furnace and vacuumizing while preserving heat; and step three, cooling the blank obtained in the step two to a third temperature under a vacuum condition, filling inert gas or nitrogen to normal pressure, and continuously cooling the blank to normal temperature. Compared with the existing purification vacuum treatment method, the oxygen content of the mixed powder in the diamond composite material blank is reduced from 600ppm to below 100ppm, the interface bonding strength of the produced diamond composite material sample is improved by 5-10%, and the high-degree purification of the whole diamond composite material blank is realized.
Description
Technical Field
The invention belongs to the technical field of diamond composite material production, and particularly relates to a heat treatment method of a diamond composite material blank, which is used for heat treatment and cleaning of the diamond composite material blank in advance before high-temperature and high-pressure synthesis.
Background
In the high-pressure high-temperature synthesis process of the diamond composite material, the gas and impurity adsorption condition of the surfaces of the diamond micro powder particles in the mixed powder of the diamond composite material blank, and the purity and oxidation condition of the bonding agent directly influence the performance of the diamond composite material. The diamond micropowder used in the diamond composite material is fine particle powder obtained by mechanically crushing diamond single crystal particles, the surface of the fine particle powder is rough and has different shapes, large surface area and high specific surface energy, and the surface of the fine particle powder is very easy to adsorb impurities such as gas, dust particles and the like; the powder granularity of the bonding agent is generally fine, the surface area is large, the specific surface energy is high, and when the air temperature is high and the humidity is high, the bonding agent is easy to oxidize, so that the heat treatment and cleaning of the mixed powder in the diamond composite material blank are very necessary before high-temperature and high-pressure synthesis.
As most diamond composite material manufacturers only carry out simple acid-base cleaning on diamond micro powder or only carry out simple vacuum heat treatment on mixed powder in a blank (for example, vacuum treatment is only carried out by using vacuum furnace equipment without introducing reductive or inert gas, the heating temperature is 450-550 ℃, and the vacuum degree is not higher than 10-3Pa), not only can the diamond micro-powder particles and the bonding agent powder be not fully reduced and cleaned, but also the oxygen content and the impurity content of the mixed powder in the blank are higher and are generally over 600 ppm; the surfaces of the hard alloy substrate and the metal cup cannot be sufficiently cleaned; leading to the participation of impurities and oxygen in reaction in the high-temperature and high-pressure synthesis process, reducing the bonding strength among diamond particles and between diamond and a bonding agent, reducing the bonding strength of a bonding interface between a diamond layer and a hard alloy substrate and reducing the capability of a metal cup for adsorbing impurity gases in mixed powder. The wear resistance and the shock resistance of the diamond composite material are influenced, and the service performance of the diamond composite material is finally influenced.
Disclosure of Invention
The invention aims to provide a heat treatment method for a diamond composite material blank, which solves the problems that the blank cannot be integrally cleaned and the performance of the produced diamond composite material is reduced due to incomplete cleaning of mixed powder in the blank in the prior art, can meet the requirement of cleaning the surface of the mixed powder in the blank, and can integrally heat-treat the cleaned blank, the oxygen content of the mixed powder in the diamond composite material blank is reduced to be lower than 100ppm, and the interface bonding strength is improved by 5-10%.
The above object of the present invention is achieved by the following technical solutions:
a heat treatment method of a diamond composite material blank sequentially comprises the following steps:
step one, a vacuum heat treatment step: placing the assembled diamond composite material blank into a vacuum furnace, heating to a first temperature under a vacuum condition, and then preserving heat for a certain time;
step two, hydrogen reduction step: continuously heating the blank obtained in the step one to a second temperature under a vacuum condition, preserving heat for a certain time, and intermittently filling hydrogen into the vacuum furnace and vacuumizing while preserving heat;
step three, protective cooling: and (4) cooling the blank obtained in the step two to a third temperature under a vacuum condition, filling inert gas or nitrogen to normal pressure, and continuously cooling the blank to normal temperature.
As a preferred embodiment, in the first step, the first temperature is 120--3Pa or less (e.g. 7 x 10)-3Pa、6*10-3Pa、5*10-3Pa、4*10-3Pa、3*10-3Pa、2*10-3Pa、1*10- 3Pa、8*10-4Pa、2*10-4Pa) is added. In the heat treatment method for the diamond composite material blank, the first step is limited within the process parameter range, so that the moisture can be fully removed and the gas can be removed, and the process efficiency is considered. More preferably, step one "said vacuum barThe specific steps of heating to a first temperature and then preserving heat for a certain time' under the condition of the parts are as follows: under the vacuum condition, firstly raising the temperature to the dehumidification drying temperature and preserving the temperature for a period of time, and then continuing raising the temperature to the degassing temperature and preserving the temperature for a period of time, wherein the dehumidification drying temperature is 120-.
In the second step, the second temperature is 500--3Pa or less (e.g. 3 x 10)-3Pa、2*10-3Pa、1*10-3Pa、4*10-4Pa、2*10-4Pa、1*10-4Pa); if the temperature is low, the reaction may be insufficient, and if the temperature is higher than 660 ℃, the powder can be agglomerated; the heat preservation time is limited in the range, so that sufficient reduction can be ensured; limiting the vacuum value to 4 x 10-3Pa or less is favorable for discharging gas generated by reduction, and re-oxidation may occur if the degree of vacuum is low; preferably, in the second step, the temperature rise rate is 3-6 ℃/min (such as 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min, 5.5 ℃/min); more preferably, the second temperature is 550 ℃ and 600 ℃ (such as 555 ℃, 560 ℃, 570 ℃, 580 ℃, 590 ℃, 595 ℃).
In the above method for heat treatment of a diamond composite blank, as a preferred embodiment, in step two, the specific processes of intermittently (also referred to as alternating) filling hydrogen and vacuuming are as follows: firstly, filling a certain amount of hydrogen into a vacuum furnace, and keeping the reduction time for 5-20min (such as 6min, 8min, 10min, 12min, 15min, 17min and 19min) after the filling is finished; then vacuumizing, and after the steps are circulated for a plurality of times, finishing vacuum reduction heat treatment and degassing treatment of the blank for a plurality of times by hydrogen, and finally finishing vacuumizing, wherein the vacuum condition in the step two is maintained; preferably, said intermittent charging is performedThe circulation times of hydrogen and vacuum treatment are 1-5 times (such as 2 times, 3 times and 4 times); more preferably, the reduction time is 10-20min (such as 11min, 12min, 14min, 16min, 18 min); the specific filling amount of the hydrogen is determined according to the mixed powder amount in the blank, and more preferably, the filling amount of the hydrogen is such that the pressure in the furnace is 1 x 104Pa-6*104Pa (e.g. 1.5 x 10)4Pa、2*104Pa、2.5*104Pa、3*104Pa、3.5*104Pa、4*104Pa、4.5*104Pa、5*104Pa、5.5*104Pa)。
In the above method for heat-treating a diamond composite material blank, as a preferred embodiment, in step three, the vacuum value is 9 x 10-4Pa or less (e.g. 8 x 10)-4Pa、7*10-4Pa、6*10-4Pa、5*10-4Pa、4*10-4Pa、3*10-4Pa、2*10- 4Pa、1*10-4Pa、8*10-5Pa), and the third temperature is 250-. If the vacuum value is less than 9 x 10-4Pa or less affects the reduction effect.
In the above method for heat-treating a diamond composite material blank, as a preferred embodiment, in the second step, the purity of the hydrogen gas introduced is 99.999% or more.
In the above method for heat-treating a diamond composite material blank, as a preferred embodiment, in step three, the purity of the inert gas or nitrogen gas introduced is 99.999% or more.
In the above method for heat-treating a diamond composite material blank, as a preferred embodiment, the diamond composite material blank before treatment comprises: the blank mixed powder layer is formed by a mixture comprising diamond micro powder and bonding agent powder, the hard alloy substrate and the first metal cup and the second metal cup; the assembly method of the diamond composite material blank comprises the following steps: firstly, spreading the blank mixed powder layer on the bottom of the first metal cup; then, filling the hard alloy substrate into the first metal cup, wherein the blank mixed powder layer is in contact with the hard alloy substrate; and thirdly, reversely covering the first metal cup with the second metal cup (namely, buckling the second metal cup on the hard alloy substrate and buckling the second metal cup with the first metal cup) to form the diamond composite blank. The diamond composite material blank is a sealed body, but gas molecules in the diamond composite material blank can escape under the condition of high vacuum degree. Preferably, the diamond composite blank further comprises: a third metal cup; the assembly method of the diamond composite material blank comprises the following steps: firstly, spreading the blank mixed powder layer on the bottom of the first metal cup; then, filling the hard alloy substrate into the first metal cup, wherein the blank mixed powder layer is in contact with the hard alloy substrate; thirdly, the second metal cup is reversely buckled to cover the first metal cup (namely, the second metal cup is buckled on the hard alloy substrate and is buckled with the first metal cup); and finally, inverting the assembly obtained in the last step, and then reversely covering the first metal cup and the second metal cup by the third metal cup (namely, buckling the third metal cup on the first metal cup and buckling the third metal cup with the second metal cup) to form the diamond composite material blank. The diamond composite material blank adopting three metal cups has more balanced tightness and internal gas molecule escape conditions, and the obtained product has better performance. More preferably, the binding agent is one or more of metal cobalt, nickel, titanium and WC, the use of the binding agent is different according to the product application and the brand, and further preferably, the material of the metal cup is high-temperature-resistant metal molybdenum, tantalum or niobium. The blank mixed powder can contain organic additives besides the diamond differential and the bonding agent, the use of the additives is determined according to the types of the added bonding agent and the mixing mode, and the liquid organic additives comprise: one or more of absolute ethyl alcohol, isopropyl ketone, ethylene glycol and glycerol; such as: dry mixed and added cobalt powder, glycerin or ethylene glycol was added, WC was added and wet mixed with absolute ethanol. The raw material formula of the blank mixed powder layer is a conventional raw material formula of a diamond composite material, and the diamond composite material is preferably a polycrystalline diamond compact.
The beneficial effects brought by the technical scheme are as follows:
1) placing the assembled diamond composite material blank into a vacuum heat treatment furnace, wherein the pressure in the furnace reaches 8 x 10- 3When the temperature is increased to 120-450 ℃ below Pa, the diamond composite material blank is subjected to dehumidification, drying and degassing treatment; the gas pressure in the furnace reaches 4 x 10-3Continuously increasing the temperature below Pa to 650 ℃ of 450-; therefore, the method not only can perform deoxidation reduction cleaning and activation on the surfaces of the diamond micro powder and the bonding agent powder, but also can perform deoxidation reduction cleaning on oxidation stains on the bonding interface of the hard alloy substrate and the surface of the metal cup, thereby realizing high cleaning treatment on the whole diamond composite material blank; inert gas or nitrogen is filled at the temperature of 150-250 ℃ to isolate the adsorption of air, thereby playing a role of protection.
Specifically, the diamond composite material blank is subjected to dehumidification, drying and degassing heat treatment at the temperature of 120-450 ℃, and the main purposes are as follows: the method comprises the following steps of firstly, preventing the oxidation of a binding agent caused by heating air contained in mixed powder in a blank, secondly, preventing the oxidation of the binding agent in the diamond composite blank caused by the conversion of water contained in the mixed powder in the blank from an adsorption state to a chemical combination state at high temperature, thirdly, removing moisture and oil dirt adsorbed on the metal cup wall and the surface of the hard alloy substrate, and preventing the pollution and the oxidation of the mixed powder in the blank in the heating process;
after the temperature is continuously raised to 450-660 ℃, high-purity hydrogen is filled to carry out repeated vacuum-reduction heat treatment on the joint surface of the diamond composite material blank mixed powder and the hard alloy substrate for many times, taking hydrogen reduction of a metal binding agent Co as an example, the reaction can be carried out at the temperature of more than 450 ℃, and the Co can be reactedxOy+yH2＝xCo+yH2O, when the temperature is lower, the reduction reaction is slow, the reduction reaction speed is accelerated along with the temperature rise, when the temperature is too high, the surface oxidation film of the metal cobalt is covered by the reduced Co and is sintered together, the hydrogen is prevented from entering to a certain degree to influence the thoroughness of reduction, and H is not favorable2Removing O; through the exploration of different process parameters, the invention determines the preferred technical parameter that the air pressure in the furnace is controlled to be 4 x 10-3The temperature of the hydrogen reduction is controlled to be 500-4-6*104Pa is proper, and the reduction time is 10-20min after the hydrogen is filled in one time;
in the process of cooling, high-purity inert gas or nitrogen is filled to carry out gas protection on mixed powder in the diamond composite material blank, and the vacuum degree is 9 x 10-4The inert gas or nitrogen is filled at the temperature of below Pa and 250-150 ℃, under the condition of negative pressure, the filled inert gas or nitrogen can be completely adsorbed around the surfaces of the powder particles in the blank, and the specific gravity of the nitrogen is equivalent to that of air and is higher than that of water vapor, so that the air is well isolated from being adsorbed on the surfaces of the powder particles again, and other inert gases do not oxidize the powder but have lighter specific gravity than that of air, and the protective barrier effect is weaker than that of nitrogen. In the present application, the vacuum degree and the gas pressure are maintained to ensure the possibility of not being oxidized again after reduction, for example, if the third temperature is set too high, the equipment is easily damaged by introducing inert gas or nitrogen, and if the third temperature is set too low, the accelerated cooling effect in the low temperature stage of 250 ℃ and 150 ℃ cannot be achieved.
2) By adopting the heat treatment method of the diamond composite material blank, the surface activity of the bonding agent is increased due to better reduction effect, and the wetting capacity of the diamond micro powder and the bonding agent is increased, so that the bonding strength is improved in the high-temperature and high-pressure synthesis process; the bonding interface of the hard alloy substrate and the diamond layer is cleaner and has no oxide interference, and the bonding strength of the substrate and the diamond layer is increased; meanwhile, the cleanness of the wall of the metal cup prevents the mixed powder in the blank from being polluted again, and the metal cup plays roles of adsorbing gas generated in high-temperature and high-pressure synthesis and shielding;
compared with the existing purification vacuum treatment method, the oxygen content of the mixed powder in the diamond composite material blank is reduced from 600ppm to below 100ppm, the interface bonding strength of the produced diamond composite material sample is improved by 5-10%, the high-degree purification of the whole diamond composite material blank is realized, the influence on the performance of the diamond composite material is reduced to the maximum extent, and the production requirement of a high-grade diamond composite material product is met.
Drawings
Fig. 1 is a schematic structural diagram of a diamond composite blank according to an embodiment of the present invention, which includes two metal cups;
fig. 2 is a schematic structural diagram of another diamond composite blank according to an embodiment of the present invention, which includes three metal cups;
in the figures, the reference numerals are explained as follows:
1-blank mixed powder layer, 2-hard alloy substrate, 3-diamond layer and substrate combination interface, 4-metal cup, 41-first metal cup, 42-second metal cup and 43-third metal cup.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
A schematic diagram of a diamond composite blank before processing in the following examples is shown in fig. 1 and 2, the blank comprises a blank mixture powder layer 1 formed by diamond micro powder and a bonding agent powder mixture, a hard alloy substrate 2 and a metal cup 4, and in the following examples, the metal cup 4 comprises a first metal cup 41, a second metal cup 42 and a third metal cup 43, which is shown in fig. 2; the assembly method of the diamond composite material blank comprises the following steps: firstly, spreading a blank mixed powder layer 1 at the bottom of a first metal cup 41; then, filling the hard alloy substrate 2 into the first metal cup 41, wherein the blank mixed powder layer 1 is in contact with the hard alloy substrate 2; thirdly, the second metal cup 42 is reversely buckled to cover the first metal cup 41, namely the second metal cup 42 is buckled on the hard alloy substrate 2 and buckled with the first metal cup 41; finally, the assembly obtained in the previous step is inverted, and the third metal cup 43 is inverted to cover the first metal cup 41 and the second metal cup 42, namely, the third metal cup 43 is buckled on the first metal cup 41 and buckled with the second metal cup 42 to form the diamond composite material blank. The diamond composite material blank is a sealing body, but gas molecules in the diamond composite material blank can escape under the condition of high vacuum degree. In production practice, the blank is inverted in the vacuum furnace during the heat treatment, i.e. the first metal cup 41 and the third metal cup 43 are below and the second metal cup 42 is above, the blank powder mixture layer 1 is below and the cemented carbide substrate 2 is above. The diamond composite material blank assembly adopts the arrangement of three layers of metal cups, namely two layers of metal cups are arranged at the position close to the blank mixed powder layer 1, so that the protection of the blank can be enhanced at high temperature and high pressure, and the flatness of the blank layer can be ensured; wherein the second metal cup plays a role in supporting the hard alloy substrate; the three layers of metal cups are buckled and sealed more closely to prevent powder leakage, and the blank mixed powder and the hard alloy substrate are connected into a more compact whole. In the diamond composite material blank in each of the following examples, two specifications of diamond fine powder, i.e., W20 diamond fine powder and W5 diamond fine powder, were used, and the binder was metal cobalt powder, in which: w20 diamond powder: w5 diamond powder: co 85:10:5 (mass ratio); the metal cup is made of high-temperature-resistant metal molybdenum. None of the raw material powders in the diamond composite blanks of the following examples were subjected to any vacuum heat treatment.
Example 1
A heat treatment method of a diamond composite blank comprises the following steps:
1) placing the diamond composite material blanks (with the size specification of phi 1613mm) assembled according to the figure 1 into a vacuum furnace, and placing 200 diamond composite material blanks in a batch in the same vacuum furnace;
2) vacuumizing the hearth to make the air pressure in the hearth reach 7.5 x 10-3The temperature is slowly increased below Pa, the temperature is increased from room temperature to 150 ℃ within 30 minutes, and the temperature is kept for half an hour; then continuing to vacuumize and heat up, and heating up to 550 ℃ within 1.5 hours, and simultaneously stabilizing the air pressure in the furnace at 4 x 10-3Pa below;
3) the temperature in the furnace is 550 ℃ and is kept for 1 hour, the vacuum furnace is intermittently filled with hydrogen and vacuumized while keeping the temperature, and the blank is subjected to degassing and reducing heat treatment integrally: firstly, filling a certain amount of hydrogen into the vacuum furnace, wherein the hydrogen filling amount enables the air pressure in the vacuum furnace to reach 3 x 104Pa (Hydrogen purity)99.999%), after 10 minutes after the end of the aeration, the vacuum is again pumped to 4 x 10-3The process is circulated for 2 times in such a way that the processes of hydrogen filling, reduction, vacuumizing, hydrogen refilling, reduction and vacuumizing are carried out in sequence during the heat preservation of the furnace at the temperature of 550 ℃ for 1 hour;
4) stopping heating, and continuously vacuumizing to 9 x 10-4Pa or less (devices shown at 9 x 10)-4Pa-5*10-4Pa interval has fluctuation), when the diamond composite material blank is cooled to 180 ℃ along with the furnace, the vacuum-pumping system is closed, nitrogen is filled to normal pressure (the purity of the nitrogen is 99.999 percent), and the blank is continuously cooled to normal temperature.
The oxygen content of the mixed powder in the ingot obtained by the heat treatment of example 1 was 98ppm as measured by an automatic nitrogen-oxygen analyzer (Beijing Steel, Minaku); comparing the bonding strength of the diamond layer in the sample after high-temperature and high-pressure synthesis with that of the interface of the hard alloy substrate: the bond strength after cleaning by heat treatment in example 1 was 5.5% higher than the bond strength obtained by simply vacuum heat treating the raw powder as described in the background art.
Example 2
A heat treatment method of a diamond composite blank comprises the following steps:
1) placing the assembled diamond composite material blanks (with the size specification of phi 1913mm and 100 pieces) shown in the figure 1 into a vacuum furnace chamber;
2) vacuumizing the hearth to make the air pressure in the hearth reach 7 x 10-3The temperature is slowly increased below Pa, the temperature is increased from room temperature to 150 ℃ within 30 minutes, and the temperature is kept for half an hour; then continuing to vacuumize and heat up, and heating up to 580 ℃ in 1.5 hours, and simultaneously stabilizing the air pressure in the furnace at 3 x 10-3Pa below;
3) keeping the temperature of 580 ℃ in the furnace for 1 hour, intermittently filling hydrogen into the vacuum furnace and vacuumizing while keeping the temperature, and degassing and reducing the whole blank: firstly, filling a certain amount of hydrogen into the vacuum furnace, wherein the hydrogen filling amount enables the air pressure in the vacuum furnace to reach 1 x 104Pa (hydrogen purity 99.999%), keeping for 10 minutes after the aeration is finished, and vacuumizing to 4 x 10-3The circulation is performed for 2 times under Pa;
4) stopping heating, and continuously vacuumizing to 9 x 10-4Pa or less (devices shown at 9 x 10)-4Pa-5*10-4Pa interval has fluctuation), when the diamond composite material blank is cooled to 200 ℃ along with the furnace, the vacuum-pumping system is closed, nitrogen is filled to normal pressure (the purity of the nitrogen is 99.999 percent), and the blank is continuously cooled to normal temperature.
The oxygen content of the mixed powder in the ingot obtained by the heat treatment of example 2 was 86ppm as measured by an automatic nitrogen-oxygen analyzer (Beijing Steel, Minnke); comparing the bonding strength of the diamond layer in the sample after high-temperature and high-pressure synthesis with that of the interface of the hard alloy substrate: the bond strength after cleaning by heat treatment in example 2 was improved by 3.5% over the bond strength obtained by simply vacuum heat treating the raw powder as described in the background art.
Example 3
A heat treatment method of a diamond composite blank comprises the following steps:
1) placing the diamond composite material blanks (with the size specification of phi 1313mm and 400 pieces) assembled according to the figure 1 into a vacuum furnace chamber;
2) vacuumizing the hearth to make the air pressure in the hearth reach 6.5 x 10-3The temperature is slowly increased from room temperature to 150 ℃ after the temperature is increased for 30 minutes below Pa (namely the first temperature), and the temperature is kept for half an hour; then, the vacuum and temperature rise were continued, and the temperature was raised to 600 c (i.e., the second temperature) over 1.5 hours while the furnace atmosphere was stabilized at 3 x 10-3Pa below;
3) keeping the temperature of the furnace at 600 ℃ for 1.5 hours, intermittently filling hydrogen into the vacuum furnace and vacuumizing while keeping the temperature, and degassing and reducing the whole blank: firstly, filling a certain amount of hydrogen into the vacuum furnace, wherein the hydrogen filling amount enables the air pressure in the vacuum furnace to reach 6 x 104Pa (hydrogen purity 99.999%), keeping for 15 minutes after the end of aeration, and vacuumizing to 3 x 10-3The circulation is performed for 3 times under Pa;
4) stopping heating, and continuously vacuumizing to 9 x 10-4Pa or less (devices shown at 9 x 10)-4Pa-5*10-4The Pa interval fluctuates, when the diamond composite material blank is cooled to 160 ℃ along with the furnace, the vacuum-pumping system is closed, and nitrogen is filled to normal pressure (filled)The purity of nitrogen is 99.999 percent), and the blank is continuously cooled to the normal temperature.
The oxygen content of the mixed powder in the ingot obtained by the heat treatment of example 3 was 90ppm as measured by an automatic nitrogen oxygen analyzer (Beijing Steel, Minnke); comparing the bonding strength of the diamond layer in the sample after high-temperature and high-pressure synthesis with that of the interface of the hard alloy substrate: the bond strength after cleaning by heat treatment in example 3 was improved by 7% over the bond strength obtained by simply vacuum heat treating the raw powder as described in the background art.
Examples 4 to 7
Examples 4 to 7 are the same as example 3 except that the first temperature and the incubation time in step 2) are different from those in example 3, and specifically, the first temperature and the incubation time in step 2) in examples 4 to 7 are shown in Table 1. The properties of the ingots obtained by the heat treatment of examples 4-7 are shown in Table 1.
TABLE 1 first temperature and incubation time and product Properties in examples 4-6, step 2)
Examples 8 to 10
Examples 8 to 10 are the same as those of example 3 except that the reduction temperature (i.e., the second temperature) and the keeping time in step 3) are different from those of example 3, and specifically, the second temperature (i.e., the reduction temperature) and the keeping time in step 3) of examples 8 to 10 are shown in Table 2. The properties of the ingots obtained by the heat treatment of examples 8-10 are shown in Table 2.
TABLE 2 second temperature and incubation time and product Properties in Steps 2) and 3) of examples 8-10
Example 11
Example 11 is the same as example 3 except that step 4) is different from example 3, and step 4) of this example is specifically as follows:
4) stopping heating, closing the vacuum-pumping system, filling nitrogen to normal pressure (the purity of the filled nitrogen is 99.999%), and cooling the blank to normal temperature.
The oxygen content of the mixed powder in the ingot obtained by the heat treatment of example 11 was 113ppm as measured by an autoanalyzer for nitrogen and oxygen (Beijing Steel, Minaku.). Comparing the bonding strength of the diamond layer in the sample after high-temperature and high-pressure synthesis with that of the interface of the hard alloy substrate: the bond strength after the heat treatment was cleaned was 3.6% higher than the bond strength obtained by simply vacuum heat treating the raw powder as described in the background art.
The above examples are given for the purpose of illustration only and are not to be construed as limiting the invention, any equivalents and modifications within the scope of the invention being included in the claims.
Claims (3)
1. A heat treatment method for a diamond composite material blank is characterized by comprising the following steps:
1) placing the assembled diamond composite material blank into a vacuum furnace chamber;
2) vacuumizing the hearth to make the air pressure in the hearth reach 6.5 x 10-3The temperature is slowly increased below Pa, the temperature is increased from room temperature to the first temperature of 150 ℃ within 30 minutes, and the temperature is kept for half an hour; then continuing to vacuumize and heat up, and heating up to the second temperature of 600 ℃ within 1.5 hours, and simultaneously stabilizing the air pressure in the furnace at 3 x 10-3Pa below;
3) keeping the temperature of the furnace at 600 ℃ for 1.5 hours, intermittently filling hydrogen into the vacuum furnace and vacuumizing while keeping the temperature, and degassing and reducing the whole blank: firstly, filling a certain amount of hydrogen into the vacuum furnace, wherein the hydrogen filling amount enables the air pressure in the vacuum furnace to reach 6 x 104Pa, the purity of hydrogen is 99.999%, after the aeration is finished, the mixture is kept for 15 minutes, and then the mixture is vacuumized to 3 x 10-3The circulation is performed for 3 times under Pa;
4) stopping heating, and continuously vacuumizing to 9 x 10-4When the diamond composite material blank is cooled to 160 ℃ along with the furnace, the vacuumizing system is closed, nitrogen is filled to normal pressure, the purity of the nitrogen is 99.999%, and the blank is continuously cooled to normal temperature;
or, the method comprises the following steps:
1) placing the assembled diamond composite material blank into a vacuum furnace chamber;
2) vacuumizing the hearth to make the air pressure in the hearth reach 6.5 x 10-3The temperature is slowly raised below Pa, the temperature is firstly raised to 150 ℃ and kept for 0.5 hour, and then the temperature is raised to 450 ℃ and kept for 1 hour; then continuing to vacuumize and heat up, and heating up to the second temperature of 600 ℃ within 1.5 hours, and simultaneously stabilizing the air pressure in the furnace at 3 x 10-3Pa below;
3) keeping the temperature of the furnace at 600 ℃ for 1.5 hours, intermittently filling hydrogen into the vacuum furnace and vacuumizing while keeping the temperature, and degassing and reducing the whole blank: firstly, filling a certain amount of hydrogen into the vacuum furnace, wherein the hydrogen filling amount enables the air pressure in the vacuum furnace to reach 6 x 104Pa, keeping for 15 minutes after the inflation is finished, and vacuumizing to 3 x 10-3The circulation is performed for 3 times under Pa;
4) stopping heating, and continuously vacuumizing to 9 x 10-4When the diamond composite material blank is cooled to 160 ℃ along with the furnace, the vacuumizing system is closed, nitrogen is filled to normal pressure, the purity of the nitrogen is 99.999%, and the blank is continuously cooled to normal temperature;
the diamond composite blank prior to treatment comprises: a blank mixed powder layer formed by a mixture of the diamond micro powder and the bonding agent powder, a hard alloy substrate, a first metal cup and a second metal cup; the assembly method of the diamond composite material blank comprises the following steps: firstly, spreading the blank mixed powder layer on the bottom of the first metal cup; then, filling the hard alloy substrate into the first metal cup, wherein the blank mixed powder layer is in contact with the hard alloy substrate; and thirdly, reversely covering the second metal cup on the first metal cup to form the diamond composite material blank.
2. The method for thermally processing a diamond composite blank according to claim 1, wherein the diamond composite blank further comprises: a third metal cup; the assembly method of the diamond composite material blank comprises the following steps: firstly, spreading the blank mixed powder layer on the bottom of the first metal cup; then, filling the hard alloy substrate into the first metal cup, wherein the blank mixed powder layer is in contact with the hard alloy substrate; thirdly, reversely buckling the second metal cup to cover the first metal cup; and finally, inverting the assembly obtained in the last step, and reversely covering the first metal cup and the second metal cup by the third metal cup to form the diamond composite material blank.
3. The method for heat treating a diamond composite blank according to claim 1, wherein the binder is one or more of metallic cobalt, nickel and titanium; the metal cup is made of high-temperature-resistant metal molybdenum, tantalum or niobium.
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