CN106756390B - A kind of hard alloy and preparation method thereof containing slab-shaped tungsten carbide crystal grain - Google Patents
A kind of hard alloy and preparation method thereof containing slab-shaped tungsten carbide crystal grain Download PDFInfo
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- CN106756390B CN106756390B CN201611085734.XA CN201611085734A CN106756390B CN 106756390 B CN106756390 B CN 106756390B CN 201611085734 A CN201611085734 A CN 201611085734A CN 106756390 B CN106756390 B CN 106756390B
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- 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
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- 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
- C22C1/055—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 carbon
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- 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
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Abstract
The invention discloses a kind of hard alloy and preparation method thereof containing slab-shaped tungsten carbide crystal grain for belonging to hard alloy technical field.The content of tungsten carbide is 78-92.2wt% in the alloy, and the content of cobalt is 7.8-22wt%, and the content of titanium carbide is 0-2wt%, and surplus is inevitable impurity；The wherein 80-95% of the total tungsten carbide volume of the volume Zhan of slab-shaped tungsten carbide crystal grain.The preparation method of the alloy is comprising steps of A) prepare prefabricated plate diamondite powder；And B) using the prefabricated plate diamondite powder of preparation further prepare the hard alloy containing slab-shaped tungsten carbide crystal grain；Wherein, raw material cobalt powder is added at one time in step A), or in two times in step A) and step B) in be separately added into.The volume fraction of plate-like shape WC grains is high in the hard alloy, and crystalline perfection is good；The simple process of the method preparation, favorable reproducibility.
Description
Technical field
The invention belongs to hard alloy technical fields, and in particular to a kind of hard alloy containing slab-shaped tungsten carbide crystal grain and its
Preparation method.
Background technique
Hard alloy has high elastic modulus, high rigidity, excellent thermal stability, high-temperature oxidation resistance and corrosion resistance,
Have in the industries such as machining, mining and widely applies.In general, the grain of tungsten carbide (WC) in change hard alloy can be passed through
Degree, cobalt (Co) content and other carbide additive amount change the hardness (i.e. wearability) and intensity and toughness of hard alloy
(i.e. break resistance), so that hard alloy be made to be widely used in various occasions.But the hardness and strength of hard alloy are (i.e. wear-resisting
Property and break resistance) be conflict parameter, performance improve will with the cost that is reduced to of another performance, and
The appearance of plate cemented carbide preferably resolves this contradiction.Plate cemented carbide, which refers in alloy, has plate brilliant special
The ratio between total volume of tungsten carbide (WC) crystal grain is greater than 20% hard alloy in the volume and alloy of tungsten carbide (WC) crystal grain of sign.
About the preparation method of plate cemented carbide, domestic there are reports.
Chinese patent CN101376931A discloses one kind using slab-shaped tungsten carbide monocrystalline as crystal seed, and WC and Co are raw material, adopts
The method for preparing hard alloy with high-energy ball milling plus vacuum-sintering.WC grain is that plate crystalline substance is mixed with what conventional grain formed in alloy
Crystal structure, as cemented carbide containing plate.The disadvantages of the method are as follows plate-like WC grain crystal grain is thicker in alloy, it is 3-8 μm, and close
The microstructure of gold is unevenly distributed, and is unfavorable for the performance of alloy property.
Wu Enxi etc. reports " research of the preparation method of hard alloy containing plate-like shape WC grains ".This report uses micron order W
Powder, Co powder and flake graphite in powder are raw material, realize that W polyhedron turns to W plate body by carrying out flaky process to W powder
Becoming, prepares cemented carbide containing plate by improving sintering temperature and extending sintering time, the WC grain of this method preparation is coarse,
It is difficult to realize the Effective Regulation to alloy microstructure uniformity and WC plate crystalline substance ratio.
Chinese patent CN102965559A discloses a kind of material of the tungsten carbide particle containing sheet and its preparation method and uses
The method of its hard alloy for preparing the tungsten carbide crystal grain containing sheet.The disadvantages of the method are as follows plate-like WC grain crystal grain in the alloy of preparation
Size distribution is uneven, and plate crystalline substance ratio is relatively low.
Pei Yanbin etc. reports " W-Co- carbon nanotubes reaction-sintered prepares height-oriented hard alloy ".This report uses
Micron order W powder, Co powder and multiple-wall carbon nanotube (diameter 10nm) are raw material, mixed using preparation in long-time wet-grinding technology and relative device (72 hours)
Close material, by the template action of carbon nanotubes realize alloy structure perpendicular to the preferred orientation of (0001) crystal face of pressing direction,
But this method is difficult to realize effective control to alloy structure structural homogeneity.
Chinese patent CN102061401B discloses one kind with W nanopowder and nano graphite powder, ultra-fine Co powder and/or Ni powder
(≤0.5 μm) is raw material, ultra-fine Cr3C2It is joint dopant with rare earth, using traditional wet-grinding technology and relative device and vacuum or pressure sintering work
Skill preparation has plate crystal structure, isotropic WC base cemented carbide.This method since the raw material of use is nanometer powder,
Its reactivity is high, and easy to oxidize during wet-milling and reunion is easy to happen WC grain abnormal growth during the sintering process, makes
Uneven at WC grain size distribution in alloy, maximum WC grain size has reached nearly 10 μm, unfavorable to the performance of alloy.
Although having three constituent element grain growth adjusting control agent of Cr+V+ rare earth in alloy, in actual industrialized production, it is difficult to realize pairing
Effective control of golden WC grain degree and microstructure uniformity.
Summary of the invention
It is a kind of containing slab-shaped tungsten carbide crystal grain the technical problem to be solved by the present invention is to provide in view of the deficiencies of the prior art
Hard alloy, the volume fraction of plate-like shape WC grains is high in the hard alloy, the 80%-95% of the total WC grain of Zhan, and crystallization is complete
Good, the even particle size distribution of WC grain of property；The microstructure of hard alloy is uniformly distributed simultaneously, and especially Binder Phase is distributed
Uniformly, intensity and fracture toughness are significantly increased.
The present invention also provides a kind of preparation method of hard alloy containing slab-shaped tungsten carbide crystal grain, the hard of this method preparation is closed
The three-dimensional appearance of WC grain is almost all plate in gold, and plate-like shape WC grains ratio is high, and the microstructure uniformity of alloy is good,
Performance is stablized, and wearability and toughness are high；And the simple process of preparation, favorable reproducibility.
For this purpose, one aspect of the present invention provides a kind of hard alloy containing slab-shaped tungsten carbide crystal grain, with hard alloy weight
Percentages comprising:
Tungsten carbide 78-92.2wt%；
Cobalt 7.8-22wt%；
Titanium carbide 0-2wt%；
Wherein, the 80%-95% of the total tungsten carbide volume of the volume Zhan of slab-shaped tungsten carbide crystal grain.
In some embodiments of the invention, the pattern of the slab-shaped tungsten carbide crystal grain is rectangle；And the rectangle
Length and wide ratio 4 or more.
Another aspect of the present invention provides a kind of preparation method of hard alloy comprising following steps:
A): preparing prefabricated plate diamondite powder；
B): further preparing the hard containing slab-shaped tungsten carbide crystal grain using the prefabricated plate diamondite powder of preparation and close
Gold.
In some embodiments of the invention, the raw material cobalt powder for preparing hard alloy is added at one time in step A), or
In two times in step A) and step B) in be separately added into.
According to the present invention, when the content of cobalt in the hard alloy is in 12wt% or less, raw material cobalt powder is in step A)
It is added at one time；When the content of cobalt in the hard alloy is greater than 12wt%, raw material cobalt powder is in two times in step A) and step
B it is separately added into), and the additional amount in step A) is not more than the 12wt% of hard alloy total weight, surplus is in step B)
It fills into.
According to the present invention, the step A) specifically includes the following steps:
S1): flaky process being carried out to raw material tungsten powder, obtains the raw material tungsten powder of flattening；
S2): the raw material tungsten powder, raw material cobalt powder and carbon source material of flattening are uniformly mixed to get raw material powder；
S3): low-temperature carbonization being carried out to raw material powder, obtains prefabricated plate diamondite powder；Wherein, the prefabricated board
There was only tungsten carbide phase and cobalt phase in shape diamondite powder.
In some embodiments of the invention, the carbon source material is flake graphite in powder；The weight of the carbon source material is
The 6.05%-6.1% of the sum of carbon source material and raw material tungsten powder weight, remaining carbon amounts are filled into using active carbon in step B).
In other embodiments of the invention, the condition of the low-temperature carbonization are as follows: temperature is 1050-1150 DEG C, atmosphere
It is lower than 20MPa for reducing atmosphere or vacuum degree.
According to the present invention, the step B) specifically includes the following steps:
T1): carrying out wet-milling after activated carbon, titanium carbide and forming agent is added in prefabricated plate diamondite powder；
T2): carrying out being spray-dried simultaneously compression moulding after wet-milling, be then sintered to obtain containing the hard of slab-shaped tungsten carbide crystal grain
Matter alloy.
In some embodiments of the invention, step T1) in, step is filled into prefabricated plate diamondite powder
S2 the raw material cobalt powder of surplus in).
In other embodiments of the invention, the forming agent is polyethylene glycol or paraffin.
The invention has the benefit that plate-like shape WC grains in the hard alloy of the present invention containing slab-shaped tungsten carbide crystal grain
Volume fraction is high, the 80%-95% of the total WC grain of Zhan, and crystalline perfection is good, the even particle size distribution of WC grain；Hard simultaneously
The microstructure of alloy is uniformly distributed, and especially Binder Phase is evenly distributed, and intensity and fracture toughness are significantly increased.This
The three-dimensional appearance of WC grain is almost all plate in the hard alloy of invention the method preparation, and plate-like shape WC grains ratio is high, closes
The microstructure uniformity of gold is good, and performance is stablized, wearability and toughness simple process that is high, and preparing, favorable reproducibility.
Detailed description of the invention
Illustrate the present invention below in conjunction with attached drawing.
Fig. 1 is the SEM shape appearance figure of raw material W powder.
Fig. 2 is the SEM shape appearance figure using W powder after the flat processing of the method for the invention.
Fig. 3 is the SEM shape appearance figure of the prefabricated plate diamondite powder obtained using the method for the invention.
Fig. 4 is the XRD spectrum of the prefabricated plate diamondite powder obtained using the method for the invention.
Fig. 5 is the SEM shape appearance figure of the hard alloy obtained using the method for the invention.
Fig. 6 is the three-dimensional appearance figure of the WC grain in the hard alloy obtained using the method for the invention.
Fig. 7 is the three-dimensional appearance figure of WC grain in ordinary rigid alloy.
Specific embodiment
To be readily appreciated that the present invention, below in conjunction with attached drawing, the present invention will be described in detail.
As previously mentioned, currently used for prepare the hard alloy containing slab-shaped tungsten carbide crystal grain method hard alloy obtained in
Plate-like WC grain crystallite size be unevenly distributed, plate crystalline substance ratio is relatively low, and the microstructure uniformity of alloy compared with
Difference.
Through research, the inventor has found that when preparing prefabricated plate WC alloy powder, by adding insufficient amount of sheet
Graphite powder fills into during subsequent wet-milling as carbon source, surplus carbon source, can effectively avoid the abnormal of WC grain and increases, makes to obtain
The WC grain even particle size distribution obtained；In addition, raw material cobalt powder is added in two times when the content of Binder Phase cobalt is more than 12wt%
Enter, so that Binder Phase is dispersed in mixing effective control, it can be achieved that alloy structure structural homogeneity in broken front and back.
The present invention is based on what the above method was made.
Therefore, the hard alloy containing slab-shaped tungsten carbide crystal grain involved in one aspect of the present invention, with hard alloy weight hundred
Divide than meter comprising:
Tungsten carbide 78-92.2wt%；
Cobalt 7.8-22wt%；
Titanium carbide 0-2wt%；
Wherein, the 80%-95% of the total tungsten carbide volume of the volume Zhan of slab-shaped tungsten carbide crystal grain, the ratio of slab-shaped tungsten carbide crystal grain
Example is high, and the microstructure uniformity of alloy is good.
In some embodiments of the invention, the pattern of the slab-shaped tungsten carbide crystal grain is rectangle；And the rectangle
Length and wide ratio 4 or more.
A kind of preparation method of the hard alloy involved in another aspect of the present invention comprising following steps:
A): preparing prefabricated plate diamondite powder；
B): further preparing the hard containing slab-shaped tungsten carbide crystal grain using the prefabricated plate diamondite powder of preparation and close
Gold.
According to the present invention, the step A) specifically includes the following steps:
S1): the raw material W powder that Fei Shi (Fsss) granularity is 2.0-6.0 μm is chosen, using hard alloy baseball, in ratio of grinding media to material
For (4-6): 1, under conditions of liquid-solid ratio is 250-300ml/kg, the flaky process of 50-70h is carried out to raw material W powder, is obtained flat
W powder after graduation；Wherein raw material W powder SEM shape appearance figure as shown in Figure 1, after flat processing W powder SEM shape appearance figure such as Fig. 2 institute
Show；
S2): the W powder after flattening is uniformly mixed to get raw material powder with raw material cobalt powder and carbon source material；Mixed process
It uses diameter for the stainless steel ball of 20mm, is (1-2): incorporation time 2-4h under conditions of 1 in ratio of grinding media to material；
In this step, if the content of cobalt is in 12wt% or less in hard alloy, raw material cobalt powder is disposable in the step
It is added；If the content of cobalt is greater than 12wt% in hard alloy, raw material cobalt powder is not greater than hard in the additional amount of the step and closes
The 12wt% of golden total weight, surplus are disposably filled into subsequent wet-milling process；Binder Phase is conducive to before broken using which
After be dispersed in mixture, realize point of effective control to Mathematical Analysis of Al-li Alloy Containing Rare Earth structural homogeneity, especially Binder Phase
Cloth；
In this step, added carbon source material is flake graphite in powder, and the weight of flake graphite in powder is flake graphite
The 6.05-6.1% of the sum of powder and raw material W powder weight, remaining carbon amounts are filled into using active carbon in subsequent wet-milling process；Due to
The activity of flake graphite in powder is lower, conducive to the formation of plate-like shape WC grains, and by adding insufficient amount of flake graphite in powder, it can be ensured that
Supplement W powder is not needed during subsequent wet-milling, effectively prevents the abnormal growth of WC grain.
S3): raw material powder low temperature under conditions of temperature is 1050-1150 DEG C, reducing atmosphere or vacuum degree are lower than 20MPa
Carbonization heat preservation 1-2h, obtains prefabricated plate diamondite powder, the SEM pattern of the prefabricated plate diamondite powder of acquisition
Figure is as shown in Figure 3；Sampling carries out W, Co and C element content analysis and X-ray diffraction analysis, prefabricated plate carbonization after being crushed to it
X-ray diffraction (XRD) map of tungsten alloy powder is as shown in figure 4, X-ray diffraction analysis result will ensure only WC phase and Co
Otherwise phase is unqualified；
In this step, when being carbonized using low-temperature carbonization method to the W powder after flaky process, carburizing temperature is set in
Between 1050-1150 DEG C, atmosphere is that reducing atmosphere or vacuum degree are lower than 20MPa, which can make the flat complete carbon of W powder
Change, almost all is converted to the form of plate-like shape WC grains, and X-ray diffraction analysis is shown, without other impurity phases, is conducive to plate crystalline substance and closes
The preparation of gold and the regulation of plate-like shape WC grains ratio.
According to the present invention, the step B) specifically includes the following steps:
T1): according to constituent content analysis as a result, hard alloy target component is compared, in prefabricated plate diamondite powder
Suitable active carbon and Co powder are filled into end, and the TiC of hard alloy total weight 0-2wt%, mixed powder adjusted is then added
End is added the binder that mass fraction is 2% and carries out wet-milling；Forming agent is one of polyethylene glycol (PEG) and paraffin, is used
Hard alloy baseball ball milling, ratio of grinding media to material are (4.5-6): 1, liquid-solid ratio 320-400ml/kg, Ball-milling Time 40-60h；
In this step, by the way that other cubic structure carbide powder TiC are added, the grain shape that can promote WC is further
To plate chip to development, conducive to the performance of alloy property；
In this step, the amount of the Co powder of supplement is the raw material cobalt powder of surplus in step S2), is closed with meeting prepared hard
The target components of gold.
T2): being spray-dried after wet-milling, then by powder pressing forming, blank after molding is pushed at 1450-1480 DEG C
Power sintering keeps the temperature 1-2h, obtains the hard alloy containing slab-shaped tungsten carbide crystal grain after cooling；The SEM pattern of the hard alloy of acquisition
Figure as shown in figure 5, the three-dimensional appearance figure of the WC grain in hard alloy as shown in fig. 6, and WC grain in ordinary rigid alloy
Three-dimensional appearance figure is as shown in Figure 7.
The present invention is scanned the instrument used when electron microscope analysis as Japan Electronics JSM6701F field emission scanning electron microscope, into
The instrument used when row X-ray diffraction analysis is Germany's D8Advance X-ray diffractometer.
Embodiment
To keep the present invention easier to understand, below in conjunction with embodiment, present invention be described in more detail, these realities
Apply example only serve it is illustrative, it is not limited to application range of the invention.If raw material used in the present invention or component nothing
Specified otherwise can be made by commercial sources or conventional method.
Embodiment 1: the preparation of the hard alloy spherical-teeth containing slab-shaped tungsten carbide crystal grain.
The ingredient of the alloy are as follows: the Co of the WC of 92.2wt%, 7.8wt% are used for rock drilling.
The preparation method is as follows:
(1) the W powder that Fsss granularity is 2-3 μm is chosen, with the ratio of grinding media to material of 6:1, the liquid-solid ratio of 300ml/kg carries out 70h's
Ball milling obtains the W powder of flattening；
(2) mixed-powder of W powder containing flattening, Co powder and flake graphite in powder is prepared, wherein the quality of Co powder is alloy
Quality 7.8wt%, quality/(W powder+flake graphite in powder) quality ratio of flake graphite in powder are 6.10%；Using stainless steel ball,
Ratio of grinding media to material is 1:1, mixes 2h, obtains uniformly mixed raw material powder；
(3) uniformly mixed raw material powder is carbonized at 1150 DEG C 1-2h in intermediate frequency furnace, obtains prefabricated slab-shaped tungsten carbide
Alloy powder；Be crushed laggard row element interpretation of result and X-ray diffraction analysis, X-ray diffraction analysis the result shows that only WC and
Co two-phase；
(4) suitable active carbon is added according to elemental analysis result, the target cobalt magnetic control of alloy between 6.6-7.0,
By gross weight be added 2wt% PEG, using hard alloy baseball carry out wet-milling, ratio of grinding media to material 4.5:1, liquid-solid ratio 320ml/kg,
Ball milling 40h；
(5) it is spray-dried after wet-milling, and compression moulding, pressed product is sintered at 1480 DEG C, kept the temperature 2h, obtain
The final hard alloy spherical-teeth containing slab-shaped tungsten carbide crystal grain；Wherein, the volume of slab-shaped tungsten carbide crystal grain accounts for tungsten carbide total volume
80%.
Embodiment 2: the preparation of the hard alloy spherical-teeth containing slab-shaped tungsten carbide crystal grain.
The ingredient of the alloy are as follows: the Co of the WC of 90wt%, 10wt% are used for rock drilling.
The preparation method is as follows:
(1) the W powder that Fsss granularity is 2-4 μm is chosen, with the ratio of grinding media to material of 5:1, the liquid-solid ratio of 275ml/kg carries out 60h's
Ball milling obtains the W powder of flattening；
(2) mixed-powder of W powder containing flattening, Co powder and flake graphite in powder is prepared, wherein the quality of Co powder is alloy
Quality 10wt%, quality/(W powder+flake graphite in powder) quality ratio of flake graphite in powder are 6.10%；Using stainless steel ball,
Ratio of grinding media to material is 1:1, mixes 2h, obtains uniformly mixed raw material powder；
(3) uniformly mixed raw material powder is carbonized at 1100 DEG C 1-2h in intermediate frequency furnace, obtains prefabricated slab-shaped tungsten carbide
Alloy powder；Be crushed laggard row element interpretation of result and X-ray diffraction analysis, X-ray diffraction analysis the result shows that only WC and
Co two-phase；
(4) suitable active carbon is added according to elemental analysis result, the target cobalt magnetic control of alloy between 8.3-9.0,
The PEG of 2wt% is added by gross weight, wet-milling, ratio of grinding media to material 5:1, liquid-solid ratio 350ml/kg, ball are carried out using hard alloy baseball
Grind 45h；
(5) it is spray-dried after wet-milling, and compression moulding, pressed product is sintered at 1450 DEG C, kept the temperature 2h, obtain
The final hard alloy spherical-teeth containing slab-shaped tungsten carbide crystal grain；Wherein, the volume of slab-shaped tungsten carbide crystal grain accounts for tungsten carbide total volume
85%.
Embodiment 3: the preparation of the hard alloy temperature upsetting mould containing slab-shaped tungsten carbide crystal grain.
The ingredient of the alloy are as follows: the TiC of the Co and 1.5wt% of the WC of 76.5wt%, 22wt%, for upsetting stainless steel spiral shell
Silk.
The preparation method is as follows:
(1) it chooses the W powder that Fsss granularity is 4-6 μm and the ball of 50h is carried out with the liquid-solid ratio of the ratio of grinding media to material 250ml/kg of 4:1
Mill, obtains the W powder of flattening；
(2) mixed-powder of W powder containing flattening, Co powder and flake graphite in powder is prepared, wherein the quality of Co powder is alloy
Quality 12wt%, quality/(W powder+flake graphite in powder) quality ratio of flake graphite in powder are 6.05%；Using stainless steel ball,
Ratio of grinding media to material is 1:1, mixes 4h, obtains uniformly mixed raw material powder；
(3) uniformly mixed raw material powder is carbonized at 1050 DEG C 1-2h in intermediate frequency furnace, obtains prefabricated slab-shaped tungsten carbide
Alloy powder；Be crushed laggard row element interpretation of result and X-ray diffraction analysis, X-ray diffraction analysis the result shows that only WC and
Co two-phase；
(4) remaining cobalt powder is added according to the target component of hard alloy, adjusts the 22wt% of Co content to alloy gross weight,
The TiC powder of alloy gross weight 1.5wt% is added, suitable active carbon, the mesh of alloy are then added according to elemental analysis result
Cobalt magnetic control is marked between 18-20, the paraffin of 2wt% is added by gross weight, wet-milling is carried out using hard alloy baseball, ratio of grinding media to material is
4.5:1, liquid-solid ratio 400ml/kg, ball milling 50h；
(5) it is spray-dried after wet-milling, and compression moulding, pressed product is sintered at 1450 DEG C, kept the temperature 1h, obtain
The final hard alloy temperature upsetting mould containing slab-shaped tungsten carbide crystal grain；Wherein, the volume of slab-shaped tungsten carbide crystal grain accounts for tungsten carbide totality
Long-pending 95%.
It should be noted that embodiment described above for explaining only the invention, is not constituted to of the invention any
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to particular case disclosed in it, on the contrary, this hair
It is bright to can be extended to other all methods and applications with the same function.
Claims (4)
1. a kind of preparation method of the hard alloy containing slab-shaped tungsten carbide crystal grain, in terms of hard alloy weight percent comprising:
Tungsten carbide 78-92.2wt%；
Cobalt 7.8-22wt%；
Titanium carbide 0-2wt%；
Wherein, the 80%-95% of the total tungsten carbide volume of the volume Zhan of slab-shaped tungsten carbide crystal grain；
The preparation method of the hard alloy the following steps are included:
A): preparing prefabricated plate diamondite powder；
B): further preparing the hard alloy containing slab-shaped tungsten carbide crystal grain using the prefabricated plate diamondite powder of preparation；
Wherein, the raw material cobalt powder for preparing hard alloy is added at one time in step A), or in two times in step A) and step B)
In be separately added into；When the content of cobalt in the hard alloy is in 12wt% or less, raw material cobalt powder disposably adds in step A)
Enter；When the content of cobalt in the hard alloy is greater than 12wt%, raw material cobalt powder is in two times in step) A and step B) in respectively
It is added, and the additional amount in step A) is not more than the 12wt% of hard alloy total weight, surplus fills into step B)；
The step A) specifically includes the following steps:
S1): flaky process being carried out to raw material tungsten powder, obtains the raw material tungsten powder of flattening；
S2): the raw material tungsten powder, raw material cobalt powder and carbon source material of flattening are uniformly mixed to get raw material powder；
S3): low-temperature carbonization being carried out to raw material powder, obtains prefabricated plate diamondite powder；Wherein, the prefabricated plate carbon
Change and there was only tungsten carbide phase and cobalt phase in tungsten alloy powder；
The carbon source material is flake graphite in powder；The quality of the carbon source material is carbon source material and raw material tungsten powder quality sum
6.05%-6.1%, remaining carbon amounts are filled into step B) using active carbon；
The step B) specifically includes the following steps:
T1): carrying out wet-milling after activated carbon, titanium carbide and forming agent is added in prefabricated plate diamondite powder；
T2): carrying out being spray-dried simultaneously compression moulding after wet-milling, be then sintered to obtain the hard containing slab-shaped tungsten carbide crystal grain and close
Gold；
Step T1) in, fill into step S2 in prefabricated plate diamondite powder) in surplus raw material cobalt powder.
2. preparation method according to claim 1, which is characterized in that the pattern of the slab-shaped tungsten carbide crystal grain is rectangular
Shape；And the rectangular length and wide ratio are 4 or more.
3. preparation method according to claim 1, which is characterized in that the condition of the low-temperature carbonization are as follows: temperature 1050-
1150 DEG C, atmosphere is that reducing atmosphere or vacuum degree are lower than 20MPa.
4. preparation method according to claim 1, which is characterized in that the forming agent is polyethylene glycol or paraffin.
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| CN102965559A (en) * | 2012-12-14 | 2013-03-13 | 株洲硬质合金集团有限公司 | Material containing sheet-shaped wolfram carbide grain and preparation method thereof as well as method for using same to prepare alloy |
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