CN104232967B - Method for preparing low binder phase wolfram carbide hard alloy - Google Patents
Method for preparing low binder phase wolfram carbide hard alloy Download PDFInfo
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Abstract
The invention provides a method for preparing a low binder phase wolfram carbide hard alloy. The method is the preparation of wolfram carbide-cobalt composite powder coated with low content of cobalt through electroless plating by sintering the powder in a spark plasma sintering furnace and includes the steps of vacuumizing to a vacuum degree of over 8Pa, pressurizing to 50MPa, heating to 1500 DEG C-1700 DEG C, depressurizing after incubation, and cooling to obtain low binder phase wolfram carbide. According to the method for preparing the low binder phase tungsten carbide hard alloy, the wolfram carbide-cobalt composite powder with low cobalt content is prepared through electroless plating, the preparation period of the powder is short, and cobalt in the form of a thin film is coated on the surface of wolfram carbide particles to be uniformly distributed and avoid local gathering of cobalt; the spark plasma sintering is used, and cobalt in liquid phase exists among all wolfram carbide particles, the bonding strength between particles is enhanced, the toughness of the alloy is improved, and the obtained hard alloy is good in material performance.
Description
Technical field
The present invention relates to hard alloy technical field, specifically, it is related to a kind of few Binder Phase Talide
Preparation method.
Background technology
Wc-co hard alloy has higher intensity, hardness, toughness and excellent wearability and decay resistance, in gold
Belong in the fields such as machining, mine probing and wear-resisting spare part and having a wide range of applications.Wherein, co has rush as Binder Phase
Enter the function of the full densification of sintering cemented carbide, and give the higher toughness of alloy and intensity, but, the raising of co content, meeting
Low-alloyed decay resistance, resistance to elevated temperatures, anti-wear performance and thermal conductivity drop, thus limiting its answering in some fields
With.Compared with common wc-co hard alloy, few Binder Phase Talide had both possessed specific to ultra-fine cemented carbide
" double high " mechanical property of high strength and high hardness, has excellent wearability and corrosion resistance again, becomes high wear resistant hard and closes
One important development direction of gold.
In the prior art, the research preparing few Binder Phase wc hard alloy is concentrated mainly on following aspect: one is to prepare
Pure wc hard alloy without any binding agent；Two is to prepare the wc hard alloy adding a small amount of co.But, few Binder Phase wc
The preparation process of hard alloy is primarily present following problem: during preparing pure wc hard alloy, due to sintering temperature mistake
High and sintering time is longer, thus hard alloy is difficult to full densification, toughness is poor；And a small amount of co is added in preparation in prior art
Wc hard alloy mainly pass through high energy ball mill method, the powder body long preparation period of the method, powder mixing is uneven, and co composition is inclined
Analysis, thus leading to wc crystal grain local anomaly in sintering process to be grown up, uneven microstructure, make alloy material mechanical property unstable,
Impact uses.Therefore, it is badly in need of developing a kind of preparation method of few Binder Phase Talide that Binder Phase is evenly distributed.
Content of the invention
Present invention aims to the deficiencies in the prior art, provide a kind of system of few Binder Phase Talide
Preparation Method, the Talide Binder Phase tissue distribution of the method preparation uniformly, has preferable toughness.On realizing
State purpose, the present invention adopts the following technical scheme that
A kind of preparation method of few Binder Phase Talide, comprises the steps:
Step one: wc powder body is added to chemical activation liquid, under room temperature, ultrasonic agitation is processed, disintegration after quiescent settling
Learn activating solution, then deionized water cleaning wc powder body；
Step 2: the wc powder body that step one is obtained adds to chemical plating fluid, is incubated to having in 70～85 DEG C of water-baths
Bubble produces, and then proceeds to 40～60 DEG C of ultrasonic ponds and carries out ultrasonic agitation chemical plating co, separation chemistry plating solution after quiescent settling, uses
Deionized water cleans powder body, obtains low cobalt content wc-co composite granule after being dried；
Step 3: the low cobalt content wc-co composite granule that step 2 is obtained is placed in discharge plasma sintering system, takes out true
Sky makes vacuum reach more than 8pa, is forced into 50mpa, is warming up to 1500～1700 DEG C of insulations, obtains few bonding after release cooling
Phase Talide.
Preferably, the crystallite dimension of described wc powder body is 0.2～0.4um.
Preferably, the ultrasonic frequency for ultrasonic agitation is 40khz, and ultrasonic power is 300～400w.
Preferably, described chemical activation liquid includes following compositions:
Preferably, wc powder body is added to chemical activation liquid by the useful load of 1kg/l.
Preferably, described chemical plating fluid includes following components:
Wherein, the ph value of described chemical plating fluid is 9～11.
Preferably, the wc powder body that step one obtains is added to chemical plating fluid by the useful load of 150g/l～1500g/l.
Preferably, in described step 2 be dried particularly as follows:
By powder body at 60～80 DEG C freeze-day with constant temperature 6h.
Preferably, the mass percent of the co included in described wc-co composite granule adopts Shimadzu (shimadzu) high
Precision (× 10-5G) analytical balance weighs and measures.
Preferably, the speed heating up in described step 3 is 200 DEG C/min, is 5 in the time of 1500～1700 DEG C of insulations
Minute.
The invention provides a kind of preparation method of few Binder Phase Talide, comprising: by wc powder body add to
In chemical activation liquid, under room temperature, ultrasonic agitation is processed, separation chemistry activating solution after quiescent settling, then deionized water cleaning wc powder
Body；Wc powder body is added to chemical plating fluid, is incubated to there being bubble to produce in 70～85 DEG C of water-baths, then proceeds to 40～60 DEG C
Ultrasonic pond carries out ultrasonic agitation chemical plating co, separation chemistry plating solution after quiescent settling, and deionized water cleans powder body, after being dried
To low cobalt content wc-co composite granule, it is subsequently placed in discharge plasma sintering system, evacuation makes vacuum reach more than 8pa,
It is forced into 50mpa, be warming up to 1500～1700 DEG C of insulations, after release cooling, obtain few Binder Phase ultrafine tungsten carbide hard alloy.
Compared with prior art, the present invention prepares low cobalt content wc-co composite granule, powder body short preparation period, co using electroless plating method
It is coated on wc particle surface in the form of knitting knitting wool thin film, is evenly distributed, there is not local co enrichment phenomenon；In sps electric discharge etc.
In ion sintering process, due to there is liquid phase co between wc granule, thus strengthening intergranular bonding strength, improve alloy
Toughness it is ensured that preparation few Binder Phase Talide there is good performance.
Brief description
Fig. 1 is wc original powder surface stereoscan photograph；
Fig. 2 is wc original powder body transmission electron microscope photo: (a) wc granule transmission electron microscope bright field image；(b) [1-210] tape spool
SEAD figure；(c) corresponding high-resolution photo；
Fig. 3 is the stereoscan photograph of chemical activation pretreated wc powder surface；
Fig. 4 is chemical activation pretreated wc powder body transmission electron microscope photo: (a) wc granule transmission electron microscope bright field image；(b)
The SEAD figure of [1-210] tape spool；(c) corresponding transmission electron microscope macrograph；The high-resolution in a region in (d) figure (c)
Photo；The high-resolution photo in b region in (e) figure (c)；The high-resolution photo in c region in (f) figure (c)；
Fig. 5 is wc-co composite granule surface scan electromicroscopic photograph.
Specific embodiment
For a further understanding of the present invention, with reference to embodiment, the preferred embodiment of the invention is described, but
It should be appreciated that these descriptions are simply to further illustrate the features and advantages of the present invention, rather than to the claims in the present invention
Limit.
The embodiment of the invention discloses a kind of preparation method of few Binder Phase Talide, comprise the steps:
Step one: wc powder body is added to chemical activation liquid, under room temperature, ultrasonic agitation is processed, disintegration after quiescent settling
Learn activating solution, then deionized water cleaning wc powder body；
Step 2: the wc powder body that step one is obtained adds to chemical plating fluid, is incubated to having in 70～85 DEG C of water-baths
Bubble produces, and then proceeds to 40～60 DEG C of ultrasonic ponds and carries out ultrasonic agitation chemical plating co, separation chemistry plating solution after quiescent settling, uses
Deionized water cleans powder body, obtains low cobalt content wc-co composite granule after being dried；
Step 3: the low cobalt content wc-co composite granule that step 2 is obtained is placed in discharge plasma sintering system, takes out true
Sky makes vacuum reach more than 8pa, is forced into 50mpa, is warming up to 1500～1700 DEG C of insulations, obtains few bonding after release cooling
Phase Talide.
According to the present invention, the crystallite dimension of described wc powder body is preferably 0.2～0.4um, more preferably 0.2～0.3um, more
It is preferably 0.2um.Preferably, wc powder body is added to chemical activation liquid by the useful load of 1kg/l.In step one and
The step all including ultrasonic agitation in step 2, the ultrasonic frequency for ultrasonic agitation is preferably 40khz, and ultrasonic power is excellent
Elect 300～400w, more preferably 350～400w, more preferably 400w as.For described step one, the time of ultrasonic agitation is excellent
Elect 15～30min, more preferably 20～30min as.Wc powder body is cleaned by deionized water, reaches the purpose of cleaning, cleaning
Number of times preferably 2～5 times, more preferably 3 times.
According to the present invention, described chemical activation liquid preferably includes following compositions:
It is furthermore preferred that described chemical activation liquid includes following compositions:
It is furthermore preferred that described chemical activation liquid includes following compositions:
Wc powder body is placed in chemical activation liquid and carries out chemical activation pretreatment it is therefore intended that making the wc powder granule surface be in
Existing micro-rough, produces the defect such as many active faults and dislocation, and induction carries out chemical plating co in active surface and strengthens
Adhesion.
Then, the wc powder body that step one obtains is added to chemical plating fluid, described chemical plating fluid preferably includes with the following group
Point:
Wherein, the ph value of described chemical plating fluid is 9～11.
It is furthermore preferred that
Wherein, the ph value of described chemical plating fluid is 10.
In mentioned component, salt based on cobaltous sulfate, sodium hypophosphite is reducing agent, and trisodium citrate is chelating agent, boric acid
For stabilizer.
Preferably, the wc powder body that step one obtains is added to chemistry by the useful load of 150g/l～1500g/l
In plating solution.There is bubble to produce in chemical plating co course of reaction, treat that bubble-free produces chemical plating co and finishes.In step 2, pass through
Deionized water cleans the purpose that powder body reaches cleaning, wash number preferably 2～5 times, more preferably 3 times.Described dry tool
Body is: by powder body at 60～80 DEG C freeze-day with constant temperature 6h.
Cobalt content≤1wt% in the low cobalt content wc-co composite granule of this step preparation, described wc-co composite granule
The mass percent of the co being comprised adopts Shimadzu (shimadzu) in high precision (× 10-5G) analytical balance weighs and measures, specifically
For: weighing the original wc powder body that is dried is w1, this wc powder body is carried out with chemical plating and coats to obtain wc-co composite granule, weigh and be dried again
Conjunction powder body is w2, and in composite granule, the quality of co is w=w2-w1, then in composite granule, the weight/mass percentage composition of co is co wt%
=(w/w2) × 100%.
The speed heating up in described step 3 is 200 DEG C/min, is 5 minutes in the time of 1500～1700 DEG C of insulations.Institute
Stating cooling step particularly as follows: cooling to less than 100 DEG C with the furnace, taking out air cooling.
The present invention prepares low cobalt content wc-co composite granule, powder body short preparation period using electroless plating method, and co is to knit knitting wool
The form of thin film is coated on wc particle surface, is evenly distributed, and there is not local co enrichment phenomenon；In sps discharge plasma sintering
During, due to there is liquid phase co between wc granule, thus strengthening intergranular bonding strength, improve the toughness of alloy,
Ensure that few Binder Phase Talide of preparation.
Few Binder Phase Talide of present invention preparation, compared with conventional rigid alloy, has high hardness, excellent
Different wearability, corrosion resistance and antioxygenic property, compared with existing few bonding phase cemented carbide, Binder Phase tissue distribution is more equal
Even, there is preferable toughness, thus greatly extending the service life in traditional field for the alloy, other necks can be become simultaneously
The succedaneum of domain traditional material.
For a further understanding of the present invention, with reference to embodiment, the technical scheme that the present invention provides is carried out specifically
Bright, protection scope of the present invention is not limited by the following examples.
The embodiment of the present invention adopt raw material and chemical reagent be commercial.
Embodiment 1
Step one: the wc powder body for 0.2um for the average grain size is added to chemical activation liquid by the useful load of 1kg/l
(40% hf40ml/l, nh4F3g/l, 65% hno330ml/l, 36%hcl20ml/l) in, ultrasonic under room temperature (40khz,
400w) stir process 15～30min；Separation chemistry activating solution after quiescent settling, then deionized water cleaning chemical activation locate in advance
Wc powder body after reason 3 times；
Step 2: the pure wc powder body of the chemical activation without co obtained by step one is placed in sps plasma discharging and burns
Clone system sintering: evacuation makes vacuum reach more than 8pa, is forced into 50mpa, with the heating rate of 200 DEG C/min to 1700
DEG C, it is incubated 5 minutes, release, cool to less than 100 DEG C taking-up air coolings with the furnace.After measured, the relative density of this sample is
98.7%, hardness is 2712hv10, and fracture toughness is 8.4mpa m1/2.
Embodiment 2
Step one: the wc powder body for 0.2um for the average grain size is added to chemical activation liquid by the useful load of 1kg/l
(40% hf40ml/l, nh4F3g/l, 65% hno330ml/l, 36%hcl20ml/l) in, ultrasonic under room temperature (40khz,
400w) stir process 15～30min；Separation chemistry activating solution after quiescent settling, then deionized water cleaning chemical activation locate in advance
Wc powder body after reason 3 times；
Step 2: pretreated for step one chemical activation wc powder body is added to chemical plating fluid by the useful load of 500g/l
In, it is incubated prior to 70～85 DEG C of water-baths, to there being bubble to produce, proceed to 40～60 DEG C of ultrasonic ponds and carry out ultrasonic (40khz, 400w)
Stirring chemical plating co, has bubble to produce in course of reaction, treat that bubble-free produces chemical plating co and finishes, separation chemistry after quiescent settling
Plating solution, then deionized water cleaning powder body 3 times, powder body are put into 60～80 DEG C of thermostatic drying chambers 6h are dried, high-precision according to Shimadzu
Degree analytical balance measures to the weighing of powder body before and after chemical plating, and the weight/mass percentage composition obtaining co in wc-co composite granule is
0.33wt%.
Described chemical plating fluid formula is as follows:
Step 3: the wc-co composite granule for 0.33wt% for the cobalt content obtained by step 2 is placed in sps electric discharge etc.
Ion sintering system sinters: evacuation makes vacuum reach more than 8pa, is forced into 50mpa, with the heating rate of 200 DEG C/min
To 1500 DEG C, it is incubated 5 minutes, release, cool to less than 100 DEG C taking-up air coolings with the furnace.After measured, the relative density of this sample is
99.5%, hardness is 2655hv10, and fracture toughness is 9.2mpa m1/2.
Respectively surface sweeping Electronic Speculum and transmission electron microscope analysis are carried out to original powder body, chemical activation pretreated wc powder body, right
Wc-co composite granule is scanned electronic microscope photos.Wherein, Fig. 1 is wc original powder surface stereoscan photograph, original powder body table
Face is more smooth；Fig. 2 is wc original powder body transmission electron microscope photo: (a) wc granule transmission electron microscope bright field image；(b) [1-210] tape spool
SEAD figure；(c) corresponding high-resolution photo.Transmission electron microscope results show, in original wc, most of granule (80%)
Middle no microstructural flaws；Fig. 3 is the stereoscan photograph of chemical activation pretreated wc powder surface, and powder surface is in micro-
See coarse, there is step dress defect；Fig. 4 is chemical activation pretreated wc powder body transmission electron microscope photo: (a) wc granule transmission
Electronic Speculum bright field image；The SEAD figure of (b) [1-210] tape spool；(c) corresponding transmission electron microscope macrograph；(d) figure (c)
The high-resolution photo in middle a region；The high-resolution photo in b region in (e) figure (c)；The high-resolution photo in c region in (f) figure (c).
Transmission electron microscope results show, in the pretreated sample of chemical activation, 70% granule carries microstructural flaws.It lacks
Sunken type is mainly fault and dislocation.As can be seen that this granule has fault horizontal and vertical in a large number from Fig. 4 (c).Right
Should be apparent that in the enlarged drawing answered that longitudinal fault { 0001 } face sliding causes, horizontal fault is that { 10-10 } face is slided
Shifting causes.Fig. 5 is wc-co composite granule surface scan electromicroscopic photograph, and co is coated on wc granule in the form of knitting knitting wool thin film
Surface, is evenly distributed.
Embodiment 3
Step one: the wc powder body for 0.2um for the average grain size is added to chemical activation liquid by the useful load of 1kg/l
(40% hf40ml/l, nh4F3g/l, 65% hno330ml/l, 36%hcl20ml/l) in, ultrasonic under room temperature (40khz,
400w) stir process 15～30min；Separation chemistry activating solution after quiescent settling, then deionized water cleaning chemical activation locate in advance
Wc powder body after reason 3 times；
Step 2: pretreated for step one chemical activation wc powder body is added to chemical plating fluid by the useful load of 250g/l
In, it is incubated prior to 70～85 DEG C of water-baths, to there being bubble to produce, proceed to 40～60 DEG C of ultrasonic ponds and carry out ultrasonic (40khz, 400w)
Stirring chemical plating co, has bubble to produce in course of reaction, treat that bubble-free produces chemical plating co and finishes, separation chemistry after quiescent settling
Plating solution, then deionized water cleaning powder body 3 times, powder body are put into 60～80 DEG C of thermostatic drying chambers 6h are dried, high-precision according to Shimadzu
Degree analytical balance measures to the weighing of powder body before and after chemical plating, and the weight/mass percentage composition obtaining co in wc-co composite granule is about
0.61wt%.
Described chemical plating fluid formula is as follows:
Step 3: by the cobalt content obtained by step 2 be 0.3wt% wc-co composite granule, be placed in sps electric discharge etc. from
Sub- sintering system sintering: evacuation makes vacuum reach more than 8pa, is forced into 50mpa, with the heating rate of 200 DEG C/min extremely
1500 DEG C, it is incubated 5 minutes, release, cool to less than 100 DEG C taking-up air coolings with the furnace.After measured, the relative density of this sample is
99.7%, hardness is 2468hv10, and fracture toughness is 9.6mpa m1/2.
Embodiment 4
Step one: the wc powder body for 0.2um for the average grain size is added to chemical activation liquid by the useful load of 1kg/l
(40% hf40ml/l, nh4F3g/l, 65% hno330ml/l, 36%hcl20ml/l) in, ultrasonic under room temperature (40khz,
400w) stir process 15～30min；Separation chemistry activating solution after quiescent settling, then deionized water cleaning chemical activation locate in advance
Wc powder body after reason 3 times；
Step 2: pretreated for step one chemical activation wc powder body is added to chemical plating fluid by the useful load of 150g/l
In, it is incubated prior to 70～85 DEG C of water-baths, to there being bubble to produce, proceed to 40～60 DEG C of ultrasonic ponds and carry out ultrasonic (40khz, 400w)
Stirring chemical plating co, has bubble to produce in course of reaction, treat that bubble-free produces chemical plating co and finishes, separation chemistry after quiescent settling
Plating solution, then deionized water cleaning powder body 3 times, powder body are put into 60～80 DEG C of thermostatic drying chambers 6h are dried, high-precision according to Shimadzu
Degree analytical balance measures to the weighing of powder body before and after chemical plating, and the weight/mass percentage composition obtaining co in wc-co composite granule is
0.98wt%.
Described chemical plating fluid formula is as follows:
Step 3: the wc-co composite granule for 0.98wt% for the cobalt content obtained by step 2 is placed in sps electric discharge etc.
Ion sintering system sinters: evacuation makes vacuum reach more than 8pa, is forced into 50mpa, with the heating rate of 100 DEG C/min
To 1500 DEG C, it is incubated 5 minutes, release, cool to less than 100 DEG C taking-up air coolings with the furnace.After measured, the relative density of this sample is
99.9%, hardness is 2409hv10, and fracture toughness is 10.4mpa m1/2.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that it is right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (5)
1. a kind of preparation method of few Binder Phase Talide is it is characterised in that comprise the steps:
Step one: wc powder body is added to chemical activation liquid by the useful load of 1kg/l, under room temperature, ultrasonic agitation is processed, static
Separation chemistry activating solution after sedimentation, then deionized water cleaning wc powder body, the crystallite dimension of described wc powder body is 0.2～0.4um；
Step 2: the wc powder body that step one is obtained is added to chemical plating fluid by the useful load of 150g/l～1500g/l, in 70
～85 DEG C of water-baths are incubated to there being bubble to produce, and then proceed to 40～60 DEG C of ultrasonic ponds and carry out ultrasonic agitation chemical plating co, static
Separation chemistry plating solution after sedimentation, deionized water cleans powder body, obtains low cobalt content wc-co composite granule after being dried；
Step 3: the low cobalt content wc-co composite granule that step 2 is obtained is placed in discharge plasma sintering system, and evacuation makes
Vacuum reaches more than 8pa, is forced into 50mpa, is warming up to 1500～1700 DEG C of insulations, obtains few Binder Phase carbon after release cooling
Change tungsten hard alloy, the speed of intensification is 200 DEG C/min, is 5 minutes in the time of 1500～1700 DEG C of insulations, described chemical plating
Liquid includes following components:
Wherein, the ph value of described chemical plating fluid is 9～11.
2. preparation method according to claim 1 it is characterised in that for ultrasonic agitation ultrasonic frequency be 40khz,
Ultrasonic power is 300～400w.
3. preparation method according to claim 1 is it is characterised in that described chemical activation liquid includes following component:
4. the preparation method according to claims 1 to 3 any one is it is characterised in that be dried concrete in described step 2
For:
By powder body at 60～80 DEG C freeze-day with constant temperature 6h.
5. the preparation method according to claims 1 to 3 any one is it is characterised in that institute in described wc-co composite granule
The mass percent of the co comprising is measured using Shimadzu high accuracy analysis balance.
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| CN106891011B (en) * | 2017-03-23 | 2019-08-02 | 洛阳理工学院 | A kind of lamination complex cutter material and preparation method |
| CN106956007B (en) * | 2017-03-23 | 2019-04-30 | 洛阳理工学院 | A kind of graded composite cutter material and preparation method |
| CN107868948A (en) * | 2017-12-01 | 2018-04-03 | 河海大学 | A kind of method of the chemical plating cobalt coated tungsten carbide based on cobalt salt activation |
| CN108165791B (en) * | 2017-12-06 | 2020-01-17 | 台州学院 | Preparation method of binderless superfine tungsten carbide hard alloy |
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