CN107557639A - A kind of three-phase structure hard alloy and preparation method thereof - Google Patents
A kind of three-phase structure hard alloy and preparation method thereof Download PDFInfo
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Abstract
A kind of three-phase structure hard alloy and preparation method thereof, it is characterised in that middle bonding phase cemented carbide is distributed in the spheric granules surface of low bonding phase cemented carbide, and high bonding phase cemented carbide is distributed in middle bonding phase cemented carbide particle surface；Bonding phase cemented carbide weight is than 62 ~ 85%, and middle bonding phase cemented carbide weight is than 5 ~ 18%, and high bonding phase cemented carbide weight is than 10 ~ 20%；145 ~ 160emu/g of low bonding phase cemented carbide magnetic saturation；140 ~ 155emu/g of middle bonding phase cemented carbide magnetic saturation；135 ~ 150emu/g of high bonding phase cemented carbide magnetic saturation；Low bonding phase cemented carbide powder and middle bonding phase cemented carbide powder dry-mixing are pelletized；Add the granulation of high bonding phase cemented carbide powder dry-mixing；Low pressure sintering obtains three-phase structure hard alloy.The present invention is used for oil carbide cylinder bits, and it is in three-decker in grainiess, and wearability is high under the premise of not broken teeth.
Description
Technical field
The invention belongs to tool materials field, and in particular to a kind of three-phase structure hard alloy and preparation method thereof, this hair
Bright three-phase structure hard alloy is applied to oil and uses post tooth.
Background technology
In general WC-Co hard alloy is using tungsten-carbide powder as main material, and cobalt powder is the alloy of bonding agent.Cobalt content and
Tungsten carbide size determines the hardness and toughness of alloy.Usual cobalt content is low, and hardness is high, and wearability is high, and toughness is low；On the contrary then phase
Instead.Under conditions of identical cobalt content, the granularity of tungsten carbide can bring certain influence to hardness, toughness, and tungsten carbide size is got over
Small, hardness is higher, and wearability is higher, and toughness is lower；It is otherwise opposite.
The toughness and wearability of existing ordinary rigid alloy are conflicts.To solve this contradiction, Chinese patent
CN101787479A discloses a kind of preparation method of hard alloy with net-shaped structure, and the alloy cobalt content is 4.2 ~ 7.5%, hardness
For HRA88.5 ~ 91.0, for mining rock drilling, drilling field, mining, oil cone bit field is not suitable for.The patent system is standby
Method is that hard alloy granule and matrix slurry mix, and easily occurs mixing uneven, granule particle fragmentation and causing honeycomb
Not prominent question.In addition, above-mentioned patent is not involved with granule, matrix magnetic saturation difference, cobalt in granule, matrix is likely to result in
Homogenization, so as to reduce honeycomb alloy property.United States Patent (USP) US5880382 discloses a kind of hard alloy with net-shaped structure, should
Alloy is to be dispersed with hard alloy granule on pure cobalt or alloy substrate, and suitable for the oil field development of high tenacity, but wearability is relatively low,
It is not suitable for mine alloy field.
The content of the invention
It is an object of the present invention to provide a kind of three-phase structure hard alloy and preparation method thereof, the weight percentage of its cobalt is
6.5 ~ 16%, hardness HRA are 86.0 ~ 90.8, for oil carbide cylinder bits, on the premise of not broken teeth, can solve ordinary rigid conjunction
The problem of golden wearability is inadequate.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：A kind of three-phase structure hard alloy, the three-phase knot
Structure hard alloy is by three kinds of low bonding phase cemented carbide, middle bonding phase cemented carbide and high bonding phase cemented carbide component structures
Into in the three-phase structure hard alloy, percentage by weight shared by the low bonding phase cemented carbide is 62 ~ 85%, in described
Percentage by weight shared by bonding phase cemented carbide be 5 ~ 18%, percentage by weight shared by the high bonding phase cemented carbide be 10 ~
20%；
Wherein, the WC grain degree of the low bonding phase cemented carbide<The WC grain degree of the middle bonding phase cemented carbide<The height
The WC grain degree of bonding phase cemented carbide；From grainiess, the low bonding phase cemented carbide distribution of particles spherical in shape, institute
State the spheric granules surface that middle bonding phase cemented carbide is distributed in low bonding phase cemented carbide, the high bonding phase cemented carbide point
Particle surface of the cloth in middle bonding phase cemented carbide；The density of the three-phase structure hard alloy is 13.90 ~ 14.95g/cm3,
Hardness HRA is 86.0 ~ 90.8, and coercive force is 65 ~ 155 Oe；
The Binder Phase Co of low bonding phase cemented carbide weight percentage be 6 ~ 14%, TaC be less than 1%, surplus WC, magnetic
Saturation is 145 ~ 160emu/g；
The Binder Phase Co of middle bonding phase cemented carbide weight percentage be 9 ~ 16%, TaC be less than 1%, surplus WC, magnetic
Saturation is 140 ~ 155emu/g；
The Binder Phase Co of high bonding phase cemented carbide weight percentage is that 12 ~ 20%, TaC is less than 1%, surplus WC,
Magnetic saturation is 135 ~ 150emu/g.
Relevant content in above-mentioned technical proposal is explained as follows：
1st, in such scheme, the grain size of the low bonding phase cemented carbide is 2 ~ 2.8 μm, and density is 14.10 ~ 15.00 g/
cm3, hardness HRA is 87.2 ~ 91.0.
2nd, in such scheme, the grain size of the middle bonding phase cemented carbide is 2.8 ~ 3.6 μm, density is 13.90 ~
14.70 g/cm3, hardness HRA is 85.5 ~ 89.5.
3rd, in such scheme, the grain size of the high bonding phase cemented carbide is 3.6 ~ 4.4 μm, density is 13.50 ~
14.40 g/cm3, hardness is HRA83.4 ~ 87.6.
4th, in such scheme, the low bonding phase cemented carbide refers to low content bonding phase cemented carbide, similarly, in glue
Content bonding phase cemented carbide during knot phase cemented carbide refers to, high bonding phase cemented carbide refer to the conjunction of high content Binder Phase hard
Gold.
To reach above-mentioned purpose, a kind of technical scheme of the preparation method for three-phase structure hard alloy that the present invention uses
It is：The preparation method in turn includes the following steps：
The first step, according to the proportioning and performance requirement of three kinds of components of the three-phase structure hard alloy of such scheme, produce respectively
Low bonding phase cemented carbide powder, middle bonding phase cemented carbide powder and high bonding phase cemented carbide powder, wherein, it is described low
Bonding phase cemented carbide powder be by raw material by proportioning successively carry out dispensing, wet-milling, add forming agent, drying and screening, granulation and
It is made；The middle bonding phase cemented carbide powder and high bonding phase cemented carbide powder are to be matched somebody with somebody raw material successively by proportioning
Material, wet-milling, be added without forming agent, drying and screening, sledge mill and be made；
Second step, the low bonding phase cemented carbide powder and middle bonding phase cemented carbide powder are subjected to dry-mixing system in proportion
Grain, middle bonding phase cemented carbide powder substantially uniformity are coated on low bonding phase cemented carbide powder particle, obtain stuff and other stuff；
3rd step, stuff and other stuff made from the second step and the high bonding phase cemented carbide powder are carried out in proportion dry-mixed
Granulation is closed, high bonding phase cemented carbide powder substantially uniformity is coated in the stuff and other stuff, obtains three component compounds；
4th step, the three components compound is subjected to low pressure sintering, sintering temperature is 1370 ~ 1460 DEG C, obtains the three-phase
Structure hard alloy.
Relevant content in above-mentioned technical proposal is explained as follows：
1st, in such scheme, the low bonding phase cemented carbide powder, middle bonding phase cemented carbide powder and high Binder Phase are hard
Binder Phase in matter alloy powder also includes Ni substitution part cobalts, percentage by weights of the Ni in Binder Phase in addition to Co
For 10% ~ 30%.
The present invention design principle and beneficial effect be：（1）The low bonding phase cemented carbide of fine grain is as core, slightly
Brilliant high bonding phase cemented carbide as matrix, and compared with coarse-grain middle bonding phase cemented carbide as mitigation transition between the two
Layer, can effectively reduce cobalt and mutually migrate, and ensure the hardness of core hard alloy and do not reduce substantially.Due to the hardness of core hard alloy
Higher, wearability is preferable；And the hardness of hard alloy substrate is low, toughness is preferable, so as to solve the wear-resisting of oil carbide cylinder bits
The problem of property and toughness contradiction.（2）It is coated between low bonding phase cemented carbide particle and high bonding phase cemented carbide particle
Middle bonding phase cemented carbide particle, the constriction coefficient between low bonding phase cemented carbide and high bonding phase cemented carbide can be reduced
Difference, so as to reduce alloy hole, improve alloy bending strength and toughness.（3）The table of the low bonding phase cemented carbide of core particle
Face is first coated with middle bonding phase cemented carbide particle, then by compound particle and matrix high bonding phase cemented carbide powder by certain ratio
Example carries out dry-mixing granulation, and matrix powder is coated on above-mentioned compound particle completely, and honeycomb is obvious, ensures that alloy substrate resists
Curved intensity.（4）The magnetic saturation of the low bonding phase cemented carbide of core is high, and the magnetic saturation of matrix high bonding phase cemented carbide is low, relaxes
In transition zone the magnetic saturation of bonding phase cemented carbide between it is above-mentioned between the two, can effectively prevent liquid phase Binder Phase from higher bonding
Phase cemented carbide migrates to relatively low bonding phase cemented carbide, reduces three kinds of alloy bondings to a certain extent and mutually homogenizes, and protects
The realization of the three-phase structure hard alloy three-decker of the present invention is demonstrate,proved.
In summary, three-phase structure hard alloy made from preparation method of the invention is used for oil carbide cylinder bits, its
It is in three-decker in grainiess, on the premise of not broken teeth, guarantee toughness, the wearability of three-phase structure hard alloy is high.
Brief description of the drawings
Accompanying drawing 1 is grainiess figure of the three-phase structure hard alloy according to made from embodiment 1 under metallographic microscope, mark
Color is most deep at number 1, is low bonding phase cemented carbide, and color is shallower at label 2, is middle bonding phase cemented carbide, face at label 3
Color is most shallow, is high bonding phase cemented carbide, from the grainiess of accompanying drawing 1, low bonding phase cemented carbide particle spherical in shape point
Cloth, middle bonding phase cemented carbide are distributed in the spheric granules surface of low bonding phase cemented carbide, high bonding phase cemented carbide distribution
In the particle surface of middle bonding phase cemented carbide.
Embodiment
Below and embodiment the invention will be further described：
Embodiment 1：Three-phase structure hard alloy-XR07F trades mark material and preparation method.
The XR07F trades mark are combined by tri- kinds of trades mark of A, B, C, and hidden hole drilling headpin tooth is used for oil.Wherein the A trades mark are used to make
Standby hard alloy granule, the C trades mark are used to prepare hard alloy substrate fine powder, the transition zone that the B trades mark are used between granule and matrix.
Its composition and performance are as shown in table 1, A：B：C percentage by weight is 8.5:0.5:1.
According to the component requirements dispensing of the material of the A trades mark in table 1, using the preparation method of conventional cemented carbide：After dispensing
The ball milling in ball mill, ratio of grinding media to material 3.5:1, abrasive media is alcohol, addition 300L/Kg, 3 ~ 6h of wet-milling.Mistake after wet-milling
300 ~ 400 eye mesh screens, re-dry, drying temperature are 80 ~ 95 DEG C.Sledge mill, briquetting, wiping sieve, granulation, sieving after drying.The A trades mark take
Performance after sample sintering is as shown in table 1.
According to the component requirements dispensing of the material of B, C trade mark in table 1, early stage preparation technology and A trade mark techniques it is essentially identical,
But forming agent is added without, without briquetting, wiping sieve, granulation, sieving after powder sledge mill.B, the performance after the sampling of the C trades mark sinters is such as
Shown in table 1.
First by A, B component mixing granulation, add component C mixing granulation and sieve, then suppress, sinter, sintering temperature
For 1440 DEG C.Final products XR07F is as shown in table 1.
The composition and performance of the XR07F alloys of table 1
Embodiment 2：Three-phase structure hard alloy-XR10F trades mark material and preparation method.
The XR10F trades mark are combined by tri- kinds of trades mark of D, E, F, for oil cone bit post tooth.Wherein the D trades mark are used to make
Standby hard alloy granule, the F trades mark are used to prepare hard alloy substrate fine powder, the transition zone that the E trades mark are used between granule and matrix.
Its composition and performance are as shown in table 2, D：E：F percentage by weights are 8:1:1.
According to the component requirements dispensing of the material of the D trades mark in table 2, using the preparation method of conventional cemented carbide：After dispensing
The ball milling in ball mill, ratio of grinding media to material 3.5:1, abrasive media is alcohol, addition 300L/Kg, wet-milling 3-6h.Mistake after wet-milling
300 ~ 400 eye mesh screens, re-dry, drying temperature are 80 ~ 95 DEG C.Sledge mill, briquetting, wiping sieve, granulation, sieving after drying.The D trades mark take
Performance after sample sintering is as shown in table 2.
According to the component requirements dispensing of the material of E, F trade mark in table 2, early stage preparation technology and A trade mark techniques it is essentially identical,
But forming agent is added without, without briquetting, wiping sieve, granulation, sieving after powder sledge mill.E, the performance after the sampling of the F trades mark sinters is such as
Shown in table 2.
First by D, component E mixing granulation, add F components mixing granulation and sieve, then suppress, sinter, sintering temperature
For 1410 DEG C.Final products XR10F is as shown in table 2.
The composition and performance of the XR10F alloys of table 2
Embodiment 3：Three-phase structure hard alloy-XR14F trades mark material and preparation method.
The XR14F trades mark by tri- kinds of trades mark of G, H, I by being combined, for oil cone bit post tooth.The wherein G trades mark are used for
Hard alloy granule is prepared, the I trades mark are used to prepare hard alloy substrate fine powder, the transition that the H trades mark are used between granule and matrix
Layer.Its composition and performance are as shown in table 3, G：H：I percentage by weights are 7.0:1.5:1.5.
According to the component requirements dispensing of the material of the G trades mark in table 3, using the preparation method of conventional cemented carbide：After dispensing
The ball milling in ball mill, ratio of grinding media to material 3.5:1, abrasive media is alcohol, addition 300L/Kg, wet-milling 3-6h.Mistake after wet-milling
300 ~ 400 eye mesh screens, re-dry, drying temperature are 80 ~ 95 DEG C.Sledge mill, briquetting, wiping sieve, granulation, sieving after drying.The G trades mark take
Performance after sample sintering is as shown in table 3.
According to the component requirements dispensing of the material of H, I trade mark in table 3, early stage preparation technology and G trade mark techniques it is essentially identical,
But but forming agent is added without, without briquetting, wiping sieve, granulation, sieving after powder sledge mill.H, the performance after I trades mark sampling sintering
As shown in table 3.
First by G, H component mixing granulation, add I components mixing granulation and sieve, then suppress, sinter, sintering temperature
For 1390 DEG C.Final products XR14F is as shown in table 3.
The composition and performance of the XR14F alloys of table 3
Implementation result
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art's energy
Solution present disclosure much of that is simultaneously implemented according to this, and it is not intended to limit the scope of the present invention.It is all spiritual according to the present invention
The equivalent change or modification that essence is made, should all be included within the scope of the present invention.
Claims (6)
- A kind of 1. three-phase structure hard alloy, it is characterised in that：The three-phase structure hard alloy by low bonding phase cemented carbide, Middle three kinds of components of bonding phase cemented carbide and high bonding phase cemented carbide are formed, in the three-phase structure hard alloy, institute It is 62 ~ 85% to state percentage by weight shared by low bonding phase cemented carbide, and percentage by weight shared by the middle bonding phase cemented carbide is 5 ~ 18%, percentage by weight shared by the high bonding phase cemented carbide is 10 ~ 20%；Wherein, the WC grain degree of the low bonding phase cemented carbide<The WC grain degree of the middle bonding phase cemented carbide<The height The WC grain degree of bonding phase cemented carbide；From grainiess, the low bonding phase cemented carbide distribution of particles spherical in shape, institute State the spheric granules surface that middle bonding phase cemented carbide is distributed in low bonding phase cemented carbide, the high bonding phase cemented carbide point Particle surface of the cloth in middle bonding phase cemented carbide；The density of the three-phase structure hard alloy is 13.90 ~ 14.95g/cm3, Hardness HRA is 86.0 ~ 90.8, and coercive force is 65 ~ 155 Oe；The Binder Phase Co of low bonding phase cemented carbide weight percentage be 6 ~ 14%, TaC be less than 1%, surplus WC, magnetic Saturation is 145 ~ 160emu/g；The Binder Phase Co of middle bonding phase cemented carbide weight percentage be 9 ~ 16%, TaC be less than 1%, surplus WC, magnetic Saturation is 140 ~ 155emu/g；The Binder Phase Co of high bonding phase cemented carbide weight percentage is that 12 ~ 20%, TaC is less than 1%, surplus WC, Magnetic saturation is 135 ~ 150emu/g.
- A kind of 2. three-phase structure hard alloy according to claim 1, it is characterised in that：The low bonding phase cemented carbide Grain size be 2 ~ 2.8 μm, density is 14.10 ~ 15.00 g/cm3, hardness HRA is 87.2 ~ 91.0.
- A kind of 3. three-phase structure hard alloy according to claim 1, it is characterised in that：The middle bonding phase cemented carbide Grain size be 2.8 ~ 3.6 μm, density is 13.90 ~ 14.70 g/cm3, hardness HRA is 85.5 ~ 89.5.
- A kind of 4. three-phase structure hard alloy according to claim 1, it is characterised in that：The high bonding phase cemented carbide Grain size be 3.6 ~ 4.4 μm, density is 13.50 ~ 14.40 g/cm3, hardness is HRA83.4 ~ 87.6.
- A kind of 5. preparation method of three-phase structure hard alloy according to claim 1 ~ 4 any one, it is characterised in that In turn include the following steps：The first step, according to the proportioning and property of three kinds of components of the three-phase structure hard alloy described in claim 1 ~ 4 any one It can require, produce low bonding phase cemented carbide powder, middle bonding phase cemented carbide powder and high bonding phase cemented carbide respectively Powder, wherein, the low bonding phase cemented carbide powder be by raw material by proportioning successively carry out dispensing, wet-milling, add forming agent, Drying and screening, granulation and be made；The middle bonding phase cemented carbide powder and high bonding phase cemented carbide powder are by raw material By proportioning successively carry out dispensing, wet-milling, be added without forming agent, drying and screening, sledge mill and be made；Second step, the low bonding phase cemented carbide powder and middle bonding phase cemented carbide powder are subjected to dry-mixing system in proportion Grain, middle bonding phase cemented carbide powder substantially uniformity are coated on low bonding phase cemented carbide powder particle, obtain stuff and other stuff；3rd step, stuff and other stuff made from the second step and the high bonding phase cemented carbide powder are carried out in proportion dry-mixed Granulation is closed, high bonding phase cemented carbide powder substantially uniformity is coated in the stuff and other stuff, obtains three component compounds；4th step, the three components compound is subjected to low pressure sintering, sintering temperature is 1370 ~ 1460 DEG C, obtains the three-phase Structure hard alloy.
- A kind of 6. preparation method of three-phase structure hard alloy according to claim 5, it is characterised in that：The low bonding Binder Phase in phase cemented carbide powder, middle bonding phase cemented carbide powder and high bonding phase cemented carbide powder is except Co In addition, Ni substitution part cobalts are also included, percentage by weights of the Ni in Binder Phase is 10% ~ 30%.
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| CN109143126A (en) * | 2018-09-20 | 2019-01-04 | 株洲硬质合金集团有限公司 | A kind of preparation method of hard alloy coercive force or magnetic saturation standard sample |
| CN109249027A (en) * | 2018-08-22 | 2019-01-22 | 株洲欧科亿数控精密刀具股份有限公司 | A kind of hard alloy numerical control blade of layer structure and preparation method thereof |
| CN111041320A (en) * | 2019-12-18 | 2020-04-21 | 江西江钨硬质合金有限公司 | Hard alloy with mixed crystal structure and preparation method thereof |
| CN111112630A (en) * | 2019-12-31 | 2020-05-08 | 潜江新锐硬质合金工具有限公司 | Granulating method for obtaining large-diameter hard alloy spherulites |
| CN111451510A (en) * | 2020-06-22 | 2020-07-28 | 苏州新锐合金工具股份有限公司 | Multi-tooth-head hard alloy composite column tooth and preparation method thereof |
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| CN111558721A (en) * | 2020-06-22 | 2020-08-21 | 苏州新锐合金工具股份有限公司 | Single-tooth-head hard alloy composite column tooth and preparation method thereof |
| CN111451510B (en) * | 2020-06-22 | 2020-09-11 | 苏州新锐合金工具股份有限公司 | Multi-tooth-head hard alloy composite column tooth and preparation method thereof |
| WO2024089236A1 (en) | 2022-10-28 | 2024-05-02 | H. C. Starck Tungsten GmbH | Granular mixture for additive manufacturing |
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