CN109136604A - A kind of preparation method of La doped hard alloy - Google Patents
A kind of preparation method of La doped hard alloy Download PDFInfo
- Publication number
- CN109136604A CN109136604A CN201710457290.6A CN201710457290A CN109136604A CN 109136604 A CN109136604 A CN 109136604A CN 201710457290 A CN201710457290 A CN 201710457290A CN 109136604 A CN109136604 A CN 109136604A
- Authority
- CN
- China
- Prior art keywords
- powder
- cobalt
- doped
- hard alloy
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
- C22C1/053—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
- C22C1/056—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using gas
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The present invention discloses a kind of preparation method of La doped hard alloy, and this method is achieved by the steps of: 1) weigh following components and matched: molybdenum powder, nickel powder, conventional silicon carbide tungsten powder, inhibitor, the cobalt powder of doped lanthanum, remaining is casting tungsten carbide powder;2) conventional silicon carbide tungsten powder and casting tungsten carbide powder are mixed and carries out ball milling;Inhibitor and the cobalt powder of doped lanthanum are mixed and carry out ball milling;3) the mixing tungsten carbide powder after ball milling and the cobalt powder of the doped lanthanum after ball milling are mixed and carries out wet-milling, obtain the first mixed slurry;4) wet-milling after mixing remaining component, obtains the second mixed slurry;5) wet-milled slurry is uniformly mixed, obtains hard alloy mixture;6) hard alloy is filtered with mixture, is dried and green compact is made in spraying granulation, the type of being then pressed into;7) green compact is sintered, kept the temperature, La doped hard alloy is made.The present invention can significantly promote the consistency and tensile strength of alloy by using the cobalt powder of doped lanthanum.
Description
Technical field
The present invention relates to cemented carbide material technical field more particularly to a kind of preparation methods of La doped hard alloy.
Background technique
Hard alloy has the spies such as high intensity, high rigidity, excellent abrasion resistance, heat resistance and good corrosion resistance
Point, and it is widely used for production wear part, cutting element, mold, mine excavation tool, geological drilling tools, oil exploitation
Tool, constitutional detail, high-temperature and high-presure resistent cylinder body and mechanical seal part etc..It is cut in petroleum, chemical industry, mine, water conservancy and metal
It cuts machine components in industry to be usually operated in corrosive environment, can be accelerated to wear by the machine components corroded, and lead to part
Premature failure, applied to the cemented carbide parts in this environment, all generally existing poor toughness, poor corrosion resistance, densification at present
Degree, the problem of tensile strength is poor, poor plasticity.
Summary of the invention
In view of this, being solved the main purpose of the present invention is to provide a kind of preparation method of La doped hard alloy
In the prior art hard alloy there is a problem of consistency and tensile strength difference.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows: a kind of preparation of La doped hard alloy
Method, this method are achieved by the steps of:
Step 1: being matched by following components in percentage by weight: molybdenum powder 6~7%, nickel powder 4~6%, conventional silicon carbide
Tungsten powder 45~50%, inhibitor 0.5~1.0%, the cobalt powder 6~8% of doped lanthanum, remaining is casting tungsten carbide powder;
Step 2: first carry out being milled to partial size being 0.3~0.8um by conventional silicon carbide tungsten powder and casting tungsten carbide powder mixing,
Mixing tungsten carbide powder after obtaining ball milling, it is spare;Inhibitor and the cobalt powder of doped lanthanum are mixed be milled to partial size be 0.2~
0.6um, the cobalt powder of the doped lanthanum after obtaining ball milling are spare;
It is added Step 3: again mixing the mixing tungsten carbide powder after the ball milling and the cobalt powder of the doped lanthanum after the ball milling
Wet-milling is carried out in ball mill, obtains the first mixed slurry;
Step 4: it is 1~2um that wet-milling to granularity in ball mill is added after remaining component is mixed, the second mixing is obtained
Slurry;
Step 5: first mixed slurry is uniformly mixed with second mixed slurry, acquisition hard alloy is used mixed
Close material;
Step 6: be filtered, be dried and spraying granulation with mixture to the hard alloy, then 450~
Compression moulding under the pressure of 470MPa, is made green compact;
Step 7: the green compact is sintered under conditions of temperature is 1370~1390 DEG C, vacuum degree is 1~2Pa, keep the temperature
La doped hard alloy is made in 3~4h.
Preferably, in the step 1, inhibitor Cr3C2、Cr3C2With VC or Cr3C2And TaC, and dosage is lower than doping
The 3% of the cobalt powder of lanthanum.
Preferably, in the step 6, the mesh number of filtering is 40~50 mesh, and drying temperature is 75~80 DEG C.
Preferably, in the step 1, the preparation method of the cobalt powder of doped lanthanum is realized by following steps:
The concentration that step 1) prepares cobalt chloride solution and ammonia that the concentration of cobalt is 107~110g/L respectively in NaOH solution tank NaOH is
The ammonium bicarbonate soln of 215~225g/L;
Lanthanum sesquioxide is added into NaOH solution tank NaOH for step 2) in cobalt chloride solution, stir evenly, and it is molten to obtain doping cobalt chloride
Liquid;
Step 3) carries out oil removing to the ammonium bicarbonate soln and doping cobalt chloride solution respectively;
Step 4) pure water of 1~2L is added into reaction kettle as bottom liquid, to heating in reaction kettle;
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously
It is added in reaction kettle, keeps the flow of doping cobalt chloride solution constant in fill process, by the stream for adjusting ammonium bicarbonate soln
Amount control pH value is 7.2~7.4, and 2~4h of reaction generates doping cobalt carbonate;
The doping cobalt carbonate is filtered by step 6), and is washed three times with 40~60 DEG C of hot water, every all over washing 20
~40min;
Step 7) is dried 10 to the doping cobalt carbonate after washing under conditions of 80~120 DEG C, -0.1~0MPa~
It is crushed 20~40s after 20h, obtains the cobaltous carbonate powder of doped lanthanum;
Step 8) by the cobaltous carbonate powder of the doped lanthanum reduction 5 at 300~400 DEG C and under conditions of being passed through hydrogen~
10h;
Doping cobaltous carbonate powder after reduction saves 12 by step 9) in nitrogen or carbon dioxide atmosphere~for 24 hours, then
It is passivated and is crushed, the cobalt powder of object-doped lanthanum is made.
Preferably, in the step 1), the preparation method of cobalt chloride solution are as follows: take a certain amount of cobalt chloride, thereto plus
Enter 50~70 DEG C of water, and stirring and dissolving, the concentration for being configured to cobalt is the cobalt chloride solution of 107~110g/L;Ammonium hydrogen carbonate
Preparation method are as follows: take a certain amount of ammonium hydrogen carbonate, 50~60 DEG C of water, and stirring and dissolving is added, the concentration for preparing ammonification is 215
The ammonium bicarbonate soln of~225g/L.
Preferably, in the step 2), the concentration of lanthanum is 1.0~5.0g/L in the doping cobalt chloride solution.
Preferably, in the step 5), when being fed with peristaltic pump, the flow for adulterating cobalt chloride is 1.5~2.5L/h, carbonic acid
The flow of hydrogen ammonium is 3~4L/h, and the reaction time is 2~4h.
Preferably, in the step 5), pH value is specially 7.3 ± 0.05.
Preferably, in the step 4), using pure water as bottom liquid, by after oil removing doping cobalt chloride solution and oil removing after
Ammonium bicarbonate soln is reacted.
Pure water is heated, bottom liquid temperature is made to reach 40~55 DEG C, by the doping cobalt chloride solution after oil removing and is being removed
Ammonium bicarbonate soln after oil is added bottom liquid and is reacted.
Compared with prior art, the present invention uses the cobalt powder of doped lanthanum, it is suppressed that conversion of the α-Co to ε-Co, significantly
Promote the toughness and wearability of hard alloy;Lanthanum may act as bonding agent, and can improve the reaction speed of tungsten chromium and carbon, shorten sintering
Time.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
A kind of preparation method of La doped hard alloy provided by the invention, this method are achieved by the steps of:
Step 1: being matched by following components in percentage by weight: molybdenum powder 6~7%, nickel powder 4~6%, conventional silicon carbide
Tungsten powder 45~50%, inhibitor 0.5~1.0%, the cobalt powder 6~8% of doped lanthanum, remaining is casting tungsten carbide powder;
Step 2: first carry out being milled to partial size being 0.3~0.8um by conventional silicon carbide tungsten powder and casting tungsten carbide powder mixing,
Mixing tungsten carbide powder after obtaining ball milling, it is spare;Inhibitor and the cobalt powder of doped lanthanum (La) are mixed carry out being milled to partial size be
0.2~0.6um, the cobalt powder of the doped lanthanum (La) after obtaining ball milling are spare;Cast tungsten carbide, phase conventional tungsten carbide have difference
Eutectic structure, the intensity of three common sinter Binder Phase and improve intergranular microstructure, improve alloy toughness and
Wearability more significantly improves the impact resistance of alloy, realizes the intensity of alloy and the matched well of microhardness, thus
So that the comprehensive performance of alloy greatly improves;Cobalt powder ball milling a few hours together with inhibitor are adulterated, inhibitor is dispersed, it will
Inhibitor is dispersed in doping cobalt powder, reduces the direct collision between ball and ball in this way, reduces the abrasion of ball and miscellaneous
The content of matter can also further refine inhibitor, more match with the granularity of ultrafine WC;
It is added Step 3: again mixing the mixing tungsten carbide powder after the ball milling and the cobalt powder of the doped lanthanum after the ball milling
Wet-milling is carried out in ball mill, obtains the first mixed slurry;
Step 4: it is 1~2um that wet-milling to granularity in ball mill is added after remaining component is mixed, the second mixing is obtained
Slurry;By wet-grinding technology and relative device, inhibitor is evenly coated at around WC under the drive of doping cobalt powder, is reached inhibitor and is being mixed
Evenly dispersed purpose in material;
Step 5: first mixed slurry is uniformly mixed with second mixed slurry, acquisition hard alloy is used mixed
Close material;
Step 6: be filtered, be dried and spraying granulation with mixture to hard alloy, then 450~
Compression moulding under the pressure of 470MPa, is made green compact;Wherein, the mesh number of filtering is 40~50 mesh, and drying temperature is 75~80 DEG C.
Step 7: green compact is sintered under conditions of temperature is 1370~1390 DEG C, vacuum degree is 1~2Pa, heat preservation 3~
La doped hard alloy is made in 4h.
Further, in step 1, the preparation method of the cobalt powder of doped lanthanum is realized by following steps:
The concentration that step 1) prepares cobalt chloride solution and ammonia that the concentration of cobalt is 107~110g/L respectively in NaOH solution tank NaOH is
The ammonium bicarbonate soln of 215~225g/L;
Specifically, the preparation method of cobalt chloride solution are as follows: take a certain amount of cobalt chloride to be put into NaOH solution tank NaOH, be added thereto
50~70 DEG C of water, and stirring and dissolving, the concentration for being configured to cobalt (Co) is the cobalt chloride solution of 107~110g/L;Ammonium hydrogen carbonate
Preparation method are as follows: take a certain amount of ammonium hydrogen carbonate to be put into another NaOH solution tank NaOH, 50~60 DEG C of water be added thereto, and
Stirring and dissolving, the concentration for preparing ammonification is the ammonium bicarbonate soln of 215~225g/L.
Lanthanum sesquioxide (La is added into NaOH solution tank NaOH for step 2) in prepared cobalt chloride solution2O3), it stirs evenly, obtains
To doping cobalt chloride solution, wherein the concentration of lanthanum (La) is 1.0~5.0g/L;
Step 3) carries out oil removing to the ammonium bicarbonate soln and doping cobalt chloride solution respectively;
The pure water that 1~2L is added into reaction kettle for step 4) is heated as bottom liquid, and to pure water, reaches bottom liquid temperature
To 40~55 DEG C, then bottom liquid is added in the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing and is reacted;
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously
It is added in reaction kettle, it is that 1.5~2.5L/h is constant that the flow of doping cobalt chloride solution is kept in fill process, by adjusting carbon
The flow of sour hydrogen ammonium salt solution is 3~4L/h to control pH value be 7.2~7.4, and 2~4h of reaction generates doping cobalt carbonate;
Step 6) is filtered cobalt carbonate is adulterated, and is washed three times with 30~60 DEG C of hot water, and every time washing 20~
40min;
Step 7) under conditions of 80~120 DEG C, -0.1~0MPa to washing after doping cobalt carbonate carry out drying 10~
It is crushed 20~40s after 20h, obtains the cobaltous carbonate powder of doped lanthanum (La);
Step 8) by the cobaltous carbonate powder of doped lanthanum (La) reduction 5 at 300~400 DEG C and under conditions of being passed through hydrogen~
10h;
The cobaltous carbonate powder of doped lanthanum (La) after reduction is saved 12 in nitrogen or carbon dioxide atmosphere by step 9)
~for 24 hours, then it is passivated and is crushed 20~40s, the cobalt powder of doped lanthanum (La) is made.
Embodiment 1
Step 1: being matched by following components in percentage by weight: molybdenum powder 6%, nickel powder 4%, conventional silicon carbide tungsten powder
45%, inhibitor 0.5%, the cobalt powder 6% of doped lanthanum, remaining is casting tungsten carbide powder;
Be milled to partial size Step 2: first mixing conventional silicon carbide tungsten powder and casting tungsten carbide powder as 0.3um, obtains ball
Mixing tungsten carbide powder after mill, it is spare;It is 0.2um that inhibitor and the cobalt powder of doped lanthanum (La), which are mixed, and be milled to partial size,
The cobalt powder of doping La after obtaining ball milling, it is spare;
It is added in ball mill Step 3: again mixing the mixing tungsten carbide powder after ball milling and the cobalt powder of the doped lanthanum after ball milling
Wet-milling is carried out, the first mixed slurry is obtained;
Step 4: it is 1um that wet-milling to granularity in ball mill is added after remaining component is mixed, the second mixing slurry is obtained
Material;
Step 5: the first mixed slurry is uniformly mixed with the second mixed slurry, hard alloy mixture is obtained;
Step 6: being filtered to hard alloy with mixture with the sieve of 40 mesh, being dried simultaneously at 75 DEG C
Spraying granulation, then the compression moulding under the pressure of 450MPa, is made green compact.
Step 7: green compact is sintered under conditions of temperature is 1370 DEG C, vacuum degree is 1Pa, 3h is kept the temperature, La doped is made
Hard alloy.
Wherein, in step 1, the preparation method of the cobalt powder of doped lanthanum passes through following steps such as and realizes:
Step 1) takes a certain amount of cobalt chloride to be put into NaOH solution tank NaOH, and 50 DEG C of water, and stirring and dissolving are added thereto, prepares
The cobalt chloride solution that concentration at cobalt (Co) is 107g/L;A certain amount of ammonium hydrogen carbonate is taken to be put into another NaOH solution tank NaOH again,
50 DEG C of water, and stirring and dissolving are added thereto, the concentration for preparing ammonification is the ammonium bicarbonate soln of 215g/L, spare;
Step 2) takes the prepared cobalt chloride solution of 3L, and 1.75gLa is added2O3, stir evenly, obtain the dense of lanthanum (La)
Degree is the doping cobalt chloride solution of 0.5g/L;
Step 3) carries out oil removing to prepared ammonium bicarbonate soln and doping cobalt chloride solution respectively;
The pure water that 1.5L is added into reaction kettle for step 4) is heated as bottom liquid, and to pure water, reaches bottom liquid temperature
To 40 DEG C, then bottom liquid is added in the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing and is reacted;
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously
It is added in reaction kettle, it is that 1.5/h is constant that the flow of doping cobalt chloride solution is kept in fill process, molten by adjusting ammonium hydrogen carbonate
The flow of liquid is 3L/h to control pH value be 7.3 ± 0.05, and reaction 2h generates doping cobalt carbonate;
Step 6) is filtered cobalt carbonate is adulterated, and is washed three times with 40 DEG C of hot water, every all over washing 20min;
Step 7) under conditions of 80 DEG C, -0.1MPa to washing after doping cobalt carbonate carry out being crushed 20s after drying 10h, obtain
The cobaltous carbonate powder of doped lanthanum (La);
Step 8) restores 5h by the cobaltous carbonate powder of doped lanthanum (La) at 300 DEG C and under conditions of being passed through hydrogen;
Step 9) saves the cobaltous carbonate powder of the doped lanthanum (La) after reduction in nitrogen or carbon dioxide atmosphere
12h, then it is passivated and is crushed 20s, the cobalt powder of doped lanthanum (La) is made.
Embodiment 2
Step 1: being matched by following components in percentage by weight: molybdenum powder 6.5%, nickel powder 5%, conventional silicon carbide tungsten powder
48%, inhibitor 0.7%, the cobalt powder 7% of doped lanthanum, remaining is casting tungsten carbide powder;
Step 2: first conventional silicon carbide tungsten powder and casting tungsten carbide powder are carried out being milled to partial size being 0.5um, after obtaining ball milling
Mixing tungsten carbide powder, it is spare;It is 0.4um that inhibitor and the cobalt powder of doped lanthanum (La), which are mixed, and be milled to partial size, is obtained
The cobalt powder of doping La after ball milling, it is spare;
It is added in ball mill Step 3: again mixing the mixing tungsten carbide powder after ball milling and the cobalt powder of the doped lanthanum after ball milling
Wet-milling is carried out, the first mixed slurry is obtained;
Step 4: it is 1.5um that wet-milling to granularity in ball mill is added after remaining component is mixed, the second mixing slurry is obtained
Material;
Step 5: the first mixed slurry is uniformly mixed with the second mixed slurry, hard alloy mixture is obtained;
Step 6: being filtered to hard alloy with mixture with the sieve of 45 mesh, being dried simultaneously at 80 DEG C
Spraying granulation, then the compression moulding under the pressure of 460MPa, is made green compact.
Step 7: green compact is sintered under conditions of temperature is 1380 DEG C, vacuum degree is 1.5Pa, 3.5h is kept the temperature, La is made
Adulterate hard alloy.
Wherein, in step 1, the preparation method of the cobalt powder of doped lanthanum passes through following steps such as and realizes:
Step 1) takes a certain amount of cobalt chloride to be put into NaOH solution tank NaOH, and 60 DEG C of water, and stirring and dissolving are added thereto, prepares
The cobalt chloride solution that concentration at cobalt (Co) is 108g/L;A certain amount of ammonium hydrogen carbonate is taken to be put into another NaOH solution tank NaOH again,
55 DEG C of water, and stirring and dissolving are added thereto, the concentration for preparing ammonification is the ammonium bicarbonate soln of 220g/L, spare;
Step 2) takes the prepared resulting cobalt chloride solution of 3L, and 10.55gLa is added2O3, stir evenly, obtain lanthanum
(La) concentration is the doping cobalt chloride solution of 3g/L (0.3%);
Step 3) carries out oil removing to prepared ammonium bicarbonate soln and doping cobalt chloride solution respectively;
The pure water that 1.5L is added into reaction kettle for step 4) is heated as bottom liquid, and to pure water, reaches bottom liquid temperature
To 40 DEG C, then bottom liquid is added in the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing and is reacted;
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously
It is added in reaction kettle, it is that 2L/h is constant that the flow of doping cobalt chloride solution is kept in fill process, molten by adjusting ammonium hydrogen carbonate
The flow of liquid is 3.5L/h to control pH value be 7.3 ± 0.05, and reaction 3h generates doping cobalt carbonate;
Step 6) is filtered cobalt carbonate is adulterated, and is washed three times with 50 DEG C of hot water, every all over washing 30min;
Step 7) under conditions of 100 DEG C, 0MPa to washing after doping cobalt carbonate carry out being crushed 40s after drying 20h and must mix
The cobaltous carbonate powder-IV of miscellaneous lanthanum (La);
Step 8) restores 10h by the cobaltous carbonate powder of doped lanthanum (La) at 400 DEG C and under conditions of being passed through hydrogen;
Step 9) saves the cobaltous carbonate powder of the doped lanthanum (La) after reduction in nitrogen or carbon dioxide atmosphere
20h, then it is passivated and is crushed 40s, the cobalt powder of doped lanthanum (La) is made.
Embodiment 3
Step 1: being matched by following components in percentage by weight: molybdenum powder 7%, nickel powder 6%, conventional silicon carbide tungsten powder
50%, inhibitor 1.0%, the cobalt powder 8% of doped lanthanum, remaining is casting tungsten carbide powder;
Step 2: first conventional silicon carbide tungsten powder and casting tungsten carbide powder are carried out being milled to partial size being 0.8m, after obtaining ball milling
Mixing tungsten carbide powder, it is spare;It is 0.6m that inhibitor and the cobalt powder of doped lanthanum (La), which are mixed, and be milled to partial size, obtains ball
The cobalt powder of doped lanthanum after mill, it is spare;
It is added in ball mill Step 3: again mixing the mixing tungsten carbide powder after ball milling and the cobalt powder of the doped lanthanum after ball milling
Wet-milling is carried out, the first mixed slurry is obtained;
Step 4: it is 2m that wet-milling to granularity in ball mill is added after remaining component is mixed, the second mixed slurry is obtained;
Step 5: the first mixed slurry is uniformly mixed with the second mixed slurry, hard alloy mixture is obtained;
Step 6: being filtered to hard alloy with mixture with 50 sieves, being dried at 80 DEG C and is sprayed
Granulation, then the compression moulding under the pressure of 480MPa, is made green compact.
Step 7: green compact is sintered under conditions of temperature is 1390 DEG C, vacuum degree is 2Pa, 4h is kept the temperature, La doped is made
Hard alloy.
Wherein, in step 1, the preparation method of the cobalt powder of doped lanthanum passes through following steps such as and realizes:
Step 1) takes a certain amount of cobalt chloride to be put into NaOH solution tank NaOH, and 60 DEG C of water, and stirring and dissolving are added thereto, prepares
The cobalt chloride solution that concentration at cobalt (Co) is 108g/L;A certain amount of ammonium hydrogen carbonate is taken to be put into another NaOH solution tank NaOH again,
55 DEG C of water, and stirring and dissolving are added thereto, the concentration for preparing ammonification is the ammonium bicarbonate soln of 220g/L, spare;
The cobalt chloride solution that step 2) takes 3L prepared, and 3.52gLa is added2O3, stir evenly, obtain lanthanum (La)
Concentration is the doping cobalt chloride solution of 1g/L (0.1%);
Step 3) carries out oil removing to prepared ammonium bicarbonate soln and doping cobalt chloride solution respectively;
The pure water that 1.5L is added into reaction kettle for step 4) is heated as bottom liquid, and to pure water, reaches bottom liquid temperature
To 50 DEG C, then bottom liquid is added in the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing and is reacted;
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously
It is added in reaction kettle, it is that 2L/h is constant that the flow of doping cobalt chloride solution is kept in fill process, molten by adjusting ammonium hydrogen carbonate
The flow of liquid is 3.5L/h to control pH value be 7.3 ± 0.05, and reaction 3h generates doping cobalt carbonate;
Step 6) is filtered cobalt carbonate is adulterated, and is washed three times with 50 DEG C of hot water, every all over washing 30min;
Step 7) is crushed under conditions of 100 DEG C, -0.05MPa to being adulterated after cobalt carbonate carries out drying 15h after washing
30s obtains the cobaltous carbonate powder of doped lanthanum;
Step 8) restores 8h by the cobaltous carbonate powder of doped lanthanum (La) at 350 DEG C and under conditions of being passed through hydrogen;
Step 9) saves the cobaltous carbonate powder of the doped lanthanum (La) after reduction in nitrogen or carbon dioxide atmosphere
15h, then it is passivated and is crushed 30s, the cobalt powder of doped lanthanum (La) is made.
Embodiment 4
Step 1: being matched by following components in percentage by weight: molybdenum powder 6.5%, nickel powder 5%, conventional silicon carbide tungsten powder
48%, inhibitor 0.7%, the cobalt powder 7% of doped lanthanum, remaining is casting tungsten carbide powder;
Step 2: first conventional silicon carbide tungsten powder and casting tungsten carbide powder are carried out being milled to partial size being 0.5um, after obtaining ball milling
Mixing tungsten carbide powder, it is spare;It is 0.4um that inhibitor and the cobalt powder of doped lanthanum (La), which are mixed, and be milled to partial size, is obtained
The cobalt powder of doping La after ball milling, it is spare;
It is added in ball mill Step 3: again mixing the mixing tungsten carbide powder after ball milling and the cobalt powder of the doped lanthanum after ball milling
Wet-milling is carried out, the first mixed slurry is obtained;
Step 4: it is 1.5um that wet-milling to granularity in ball mill is added after remaining component is mixed, the second mixing slurry is obtained
Material;
Step 5: the first mixed slurry is uniformly mixed with the second mixed slurry, hard alloy mixture is obtained;
Step 6: being filtered to hard alloy with mixture with the sieve of 45 mesh, being dried simultaneously at 80 DEG C
Spraying granulation, then the compression moulding under the pressure of 460MPa, is made green compact.
Step 7: green compact is sintered under conditions of temperature is 1380 DEG C, vacuum degree is 1.5Pa, 3.5h is kept the temperature, La is made
Adulterate hard alloy.
Wherein, in step 1, the preparation method of the cobalt powder of doped lanthanum passes through following steps such as and realizes:
Step 1) takes a certain amount of cobalt chloride to be put into NaOH solution tank NaOH, and 70 DEG C of water, and stirring and dissolving are added thereto, prepares
The cobalt chloride solution that concentration at cobalt (Co) is 110g/L;A certain amount of ammonium hydrogen carbonate is taken to be put into another NaOH solution tank NaOH again,
60 DEG C of water, and stirring and dissolving are added thereto, the concentration for preparing ammonification is the ammonium bicarbonate soln of 225g/L, spare;
The cobalt chloride solution that step 2) takes 3L prepared, and 5.27gLa is added2O3, stir evenly, obtain lanthanum (La)
Concentration is the doping cobalt chloride solution of 1.5g/L;
Step 3) carries out oil removing to prepared ammonium bicarbonate soln and doping cobalt chloride solution respectively;
The pure water that 1.5L is added into reaction kettle for step 4) is heated as bottom liquid, and to pure water, reaches bottom liquid temperature
To 55 DEG C, then bottom liquid is added in the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing and is reacted;
Step 5) is fed with peristaltic pump, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln simultaneously
It is added in reaction kettle, it is 2.5 constant that the flow of doping cobalt chloride solution is kept in fill process, by adjusting ammonium bicarbonate soln
Flow be 4L/h to control pH value be 7.3 ± 0.05, reaction 4h generates doping cobalt carbonate;
Step 6) is filtered cobalt carbonate is adulterated, and is washed three times with 60 DEG C of hot water, every all over washing 40min;
Step 7) under conditions of 120 DEG C, 0MPa to washing after doping cobalt carbonate carry out being crushed 40s after drying 20h and must mix
The cobaltous carbonate powder-III of miscellaneous lanthanum (La);
Step 8) restores 10h by the cobaltous carbonate powder of doped lanthanum (La) at 400 DEG C and under conditions of being passed through hydrogen;
Step 9) saves the cobaltous carbonate powder of the doped lanthanum (La) after reduction in nitrogen or carbon dioxide atmosphere
20h, then it is passivated and is crushed 40s, the cobalt powder of doped lanthanum (La) is made.
Compared with the existing technology, when the cobalt powder of doped lanthanum of the present invention (La) is applied in hard alloy, in Co phase dissolved with
W, WC, doped chemical chromium, these doped chemical chromium segregations improve the stacking fault energy of dislocation in the dislocation of Co phase, hinder dislocation into
Line width is decomposed, thus reduces the width of fault, that is, reduces potential ε-Co plumule, while W, WC, doped chemical have
" pinning " effect, keeps plumule not easily shifted, when the temperature increases, so that α-Co be inhibited to improve γ phase to the transformation of ε-Co
The content of middle α-Co, improves the toughness of alloy;Cobalt may act as bonding agent, and can improve the reaction speed of tungsten chromium and carbon, shorten
Sintering time.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the scope of the present invention.
Claims (10)
1. a kind of preparation method of La doped hard alloy, which is characterized in that this method is achieved by the steps of:
Step 1: being matched by following components in percentage by weight: molybdenum powder 6~7%, nickel powder 4~6%, conventional silicon carbide tungsten powder
45~50%, inhibitor 0.5~1.0%, the cobalt powder 6~8% of doped lanthanum, remaining is casting tungsten carbide powder;
Be milled to partial size Step 2: first mixing conventional silicon carbide tungsten powder and casting tungsten carbide powder as 0.3~0.8um, obtains
Mixing tungsten carbide powder after ball milling, it is spare;Inhibitor and the cobalt powder of doped lanthanum are mixed be milled to partial size be 0.2~
0.6um, the cobalt powder of the doped lanthanum after obtaining ball milling are spare;
Ball milling is added Step 3: again mixing the mixing tungsten carbide powder after the ball milling and the cobalt powder of the doped lanthanum after the ball milling
Wet-milling is carried out in machine, obtains the first mixed slurry;
Step 4: it is 1~2um that wet-milling to granularity in ball mill is added after remaining component is mixed, the second mixed slurry is obtained;
Step 5: first mixed slurry is uniformly mixed with second mixed slurry, hard alloy mixture is obtained;
Step 6: be filtered, be dried and spraying granulation with mixture to the hard alloy, then 450~
Compression moulding under the pressure of 470MPa, is made green compact;
Step 7: the green compact is sintered under conditions of temperature is 1370~1390 DEG C, vacuum degree is 1~2Pa, heat preservation 3~
La doped hard alloy is made in 4h.
2. a kind of preparation method of La doped hard alloy according to claim 1, which is characterized in that the step 1
In, inhibitor Cr3C2、Cr3C2With VC or Cr3C2And TaC, and dosage is lower than the 3% of the cobalt powder of doped lanthanum.
3. a kind of preparation method of La doped hard alloy according to claim 1, which is characterized in that the step 6
In, the mesh number of filtering is 40~50 mesh, and drying temperature is 75~80 DEG C.
4. a kind of preparation method of La doped hard alloy according to claim 1, which is characterized in that the step 1
In, the preparation method of the cobalt powder of doped lanthanum is realized by following steps:
The concentration that step 1) prepares cobalt chloride solution and ammonia that the concentration of cobalt is 107~110g/L respectively in NaOH solution tank NaOH is 215
The ammonium bicarbonate soln of~225g/L;
Lanthanum sesquioxide is added into NaOH solution tank NaOH for step 2) in cobalt chloride solution, stir evenly, and obtains doping cobalt chloride solution;
Step 3) carries out oil removing to the ammonium bicarbonate soln and doping cobalt chloride solution respectively;
Step 4) pure water of 1~2L is added into reaction kettle as bottom liquid, to heating in reaction kettle;
Step 5) is fed with peristaltic pump, and the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing are added simultaneously
Keep the flow of doping cobalt chloride solution constant in reaction kettle, in fill process, by the flow control for adjusting ammonium bicarbonate soln
PH value processed is 7.2~7.4, and 2~4h of reaction generates doping cobalt carbonate;
The doping cobalt carbonate is filtered by step 6), and is washed three times with 40~60 DEG C of hot water, and every time washing 20~
40min;
After 10~20h is dried to the doping cobalt carbonate after washing under conditions of 80~120 DEG C, -0.1~0MPa in step 7)
Broken 20~40s, obtains the cobaltous carbonate powder of doped lanthanum;
Step 8) restores 5~10h by the cobaltous carbonate powder of the doped lanthanum at 300~400 DEG C and under conditions of being passed through hydrogen;
Doping cobaltous carbonate powder after reduction saves 12 by step 9) in nitrogen or carbon dioxide atmosphere~for 24 hours, then carry out
It is passivated and is crushed, the cobalt powder of object-doped lanthanum is made.
5. a kind of preparation method of La doped hard alloy according to claim 4, which is characterized in that the step 1)
In, the preparation method of cobalt chloride solution are as follows: a certain amount of cobalt chloride is taken, 50~70 DEG C of water, and stirring and dissolving are added thereto,
The concentration for being configured to cobalt is the cobalt chloride solution of 107~110g/L;The preparation method of ammonium hydrogen carbonate are as follows: take a certain amount of bicarbonate
50~60 DEG C of water, and stirring and dissolving is added in ammonium, and the concentration for preparing ammonification is the ammonium bicarbonate soln of 215~225g/L.
6. a kind of preparation method of La doped hard alloy according to claim 4, which is characterized in that the step 2)
In, the concentration of lanthanum is 1.0~5.0g/L in the doping cobalt chloride solution.
7. a kind of preparation method of La doped hard alloy according to claim 4, which is characterized in that the step 5)
In, when being fed with peristaltic pump, the flow for adulterating cobalt chloride is 1.5~2.5L/h, and the flow of ammonium hydrogen carbonate is 3~4L/h, described
Reaction time is 2~4h.
8. a kind of preparation method of La doped hard alloy according to claim 4, which is characterized in that the step 5)
In, pH value is specially 7.3 ± 0.05.
9. a kind of preparation method of La doped hard alloy according to claim 4, which is characterized in that the step 4)
In, using pure water as bottom liquid, the doping cobalt chloride solution after oil removing and the ammonium bicarbonate soln after oil removing are reacted.
10. a kind of preparation method of La doped hard alloy according to claim 9, which is characterized in that carried out to pure water
Heating, so that bottom liquid temperature is reached 40~55 DEG C, by after oil removing doping cobalt chloride solution and oil removing after ammonium bicarbonate soln
Bottom liquid is added to be reacted.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710457290.6A CN109136604B (en) | 2017-06-16 | 2017-06-16 | Preparation method of lanthanum-doped hard alloy |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710457290.6A CN109136604B (en) | 2017-06-16 | 2017-06-16 | Preparation method of lanthanum-doped hard alloy |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109136604A true CN109136604A (en) | 2019-01-04 |
CN109136604B CN109136604B (en) | 2020-09-29 |
Family
ID=64830451
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710457290.6A Active CN109136604B (en) | 2017-06-16 | 2017-06-16 | Preparation method of lanthanum-doped hard alloy |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109136604B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114752801A (en) * | 2022-05-12 | 2022-07-15 | 崇义章源钨业股份有限公司 | Plate-shaped crystal reinforced net-shaped structure hard alloy and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07197180A (en) * | 1993-12-29 | 1995-08-01 | Kobe Steel Ltd | High strength and high hardness sintered hard alloy excellent in corrosion resistance |
CN102031436A (en) * | 2011-01-17 | 2011-04-27 | 中南大学 | Method for improving corrosion resistance of WC-Co hard alloy |
CN104831098A (en) * | 2014-02-11 | 2015-08-12 | 中国科学院金属研究所 | Preparation method of WC-Co hard alloy with in-situ addition of rare earth oxide crystal grain refiner |
CN105970062A (en) * | 2016-05-18 | 2016-09-28 | 湖南世纪钨材股份有限公司 | Abrasion-resistant hard alloy and preparation method thereof |
-
2017
- 2017-06-16 CN CN201710457290.6A patent/CN109136604B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07197180A (en) * | 1993-12-29 | 1995-08-01 | Kobe Steel Ltd | High strength and high hardness sintered hard alloy excellent in corrosion resistance |
CN102031436A (en) * | 2011-01-17 | 2011-04-27 | 中南大学 | Method for improving corrosion resistance of WC-Co hard alloy |
CN104831098A (en) * | 2014-02-11 | 2015-08-12 | 中国科学院金属研究所 | Preparation method of WC-Co hard alloy with in-situ addition of rare earth oxide crystal grain refiner |
CN105970062A (en) * | 2016-05-18 | 2016-09-28 | 湖南世纪钨材股份有限公司 | Abrasion-resistant hard alloy and preparation method thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114752801A (en) * | 2022-05-12 | 2022-07-15 | 崇义章源钨业股份有限公司 | Plate-shaped crystal reinforced net-shaped structure hard alloy and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN109136604B (en) | 2020-09-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2017070993A1 (en) | Alloy drill and manufacturing method thereof | |
WO2017127950A1 (en) | Molten salt chemical method for recovering waste hard alloy | |
CN104962793B (en) | Polycrystalline diamond compact with excellent electric conductivity and method for manufacturing polycrystalline diamond compact | |
CN102031367B (en) | A kind of method of Leaching Vanadium from vanadium-containing shale ore deposit | |
Katiyar et al. | An overview on different processes for recovery of valuable metals from tungsten carbide scrap. | |
CN107630146A (en) | nickel recovery method | |
CN102925695A (en) | Method for leaching nickel (Ni) and cobalt (Co) from waste high-temperature alloy material | |
CN102974818B (en) | Formula and manufacturing method for special diamond tool bit | |
CN105112726A (en) | Nickel-based ceramic cylinder sleeve and powder metallurgy preparation method thereof | |
CN111334666A (en) | Method for comprehensively utilizing valuable elements in ultrasonic leaching high-temperature alloy waste | |
CN103334017A (en) | Method for preparing high-purity nickel powder from waste high-temperature alloy | |
CN109136602A (en) | A kind of preparation method of chromium doping hard alloy | |
CN109706340A (en) | A kind of fine-granularity diamond plycrystalline diamond and preparation method thereof | |
CN109136604A (en) | A kind of preparation method of La doped hard alloy | |
CN109628744A (en) | A method of recycling tungsten and cobalt from tungstenic waste hand alloy material | |
CN111979462A (en) | WC-MoC-Co-Y2O3 hard alloy with high hardness and preparation method thereof | |
CN109136603A (en) | A kind of preparation method of aluminium doping hard alloy | |
CN111636024A (en) | WC-Ni-Cr/Ta composite material hard alloy and preparation method and application thereof | |
CN109778046B (en) | Preparation method of low-cost high-performance WC-Co hard alloy with mixed crystal structure | |
GB2625232A (en) | Method for recovering carbide from waste TI(C,N)-based metal ceramic | |
CN106735244A (en) | A kind of oil field with WC Co hard alloy series tooth preparation method | |
CN104099478B (en) | A kind of method reclaiming and prepare chromium metal | |
CN105331811A (en) | Method for extracting tantalum, niobium and rare earth elements in multi-metal associated tantalum-niobium ores | |
CN109750167A (en) | A method of recycling nickel from nickel base superalloy waste cut materials | |
CN103305712A (en) | Production method of titanium carbide-based hard alloy |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right |
Effective date of registration: 20220304 Address after: 448124 No. 8, Changqing Road, Duodao District, Jingmen City, Hubei Province (Hubei lvwu) Patentee after: Hubei green Tungsten Resource Recycling Co.,Ltd. Address before: 448124 Jingmen high tech Industrial Development Zone, Jingmen, Hubei Patentee before: JINGMEN GEM Co.,Ltd. |
|
TR01 | Transfer of patent right |