CN113502426A - Multi-grain-size hard alloy and preparation method thereof - Google Patents
Multi-grain-size hard alloy and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of hard alloy preparation, and particularly relates to a hard alloy with multiple grain sizes and a preparation method thereof. Weighing a certain amount of Co powder, WC powder, amorphous alloy powder and a forming agent according to the proportion of target alloy components, uniformly mixing, and preparing the novel hard alloy containing the micron-submicron-nanometer multi-scale structure by a two-step multi-physical-field coupling rapid sintering technology of pre-sintering and densification sintering. The pre-sintering is superplastic hot-pressing sintering, the initial bonding is realized by utilizing the superplasticity of the amorphous alloy in a supercooled liquid phase region, the amorphous alloy is used as a bonding phase, the densification sintering time is reduced, and the growth of WC grains is avoided; the densification sintering is liquid phase sintering with Co as a binder phase, so that raw material powder is further bonded, W-rich nanocrystalline is crystallized and precipitated from the amorphous alloy, beneficial elements or compounds thereof are introduced to form the hard alloy with the multi-grain size, and the comprehensive performance of the hard alloy is improved.
Description
Technical Field
The invention belongs to the technical field of hard alloy preparation, and particularly relates to a hard alloy with multiple grain sizes and a preparation method thereof.
Background
The hard alloy has cermet materials with high hardness and high wear resistance, is known as 'industrial teeth', becomes an indispensable key material for the development of modern industrial society, and is widely applied to various fields of automobile industry, aerospace, integrated circuit manufacturing and the like. However, cemented carbides, which mainly contain Co as a binder phase, are also an opportunity and challenge. As a strategic resource, the consumption of Co is aggravated due to the great popularization of lithium batteries, China is gradually becoming the largest producing country and the main consuming country for refining Co all over the world, on the contrary, China is a poor Co country and only accounts for 1% of the world reserves and relies on import for a long time, so that the cemented carbide is expensive and difficult to industrially produce in large scale, and therefore, the Co is replaced by Ni, intermetallic compounds, high-entropy alloys and the like, rare earth elements and compounds thereof are used, and even the improvement of the performance of the cemented carbide by adjusting a process method is an important direction for the development of the cemented carbide.
However, these methods simultaneously face several problems: (1) patent No. CN 111254336A, adding NiCl2·6H2When the O is used as a sintering aid to replace Co to prepare WC-Ni hard alloy, the heating temperature is as high as 1400-2000 ℃, the heating time is 30-200 min, the coarsening of WC crystal grains is seriously aggravated, and in addition, the solubility of WC in Ni is high, so that the defects of pores, nickel pools and the like are easily generated after the hard alloy is sintered; (2) the addition of rare earths and their compounds does refine the grains: patent No. CN 111057928A, adding Y2O3The WC crystal grains can be refined through dispersion strengthening, the alloy performance is improved, however, Y2O3The addition of (2) does not reduce the use amount of Co, and simultaneously reduces the thermoplasticity and the obdurability; patent No. CN 109468516A by adding small amount of rare earth elementsThe growth of crystal grains can be obviously inhibited, but the uniform dispersion is difficult to ensure, and the oxidation is easy to occur in the sintering process; (3) the invention patent with the patent number of CN110438384A prepares an iron-nickel-based ultrafine grain hard alloy which can improve the obdurability, but for directly added aluminum powder, burning loss can occur in the sintering process, and the utilization rate is difficult to ensure, so that direct addition of compounds is required to be considered to avoid burning loss; (4) the addition of transition metal carbide can inhibit the growth of WC crystal grains: the literature "Bouleghlem M, Zahzoh M, Hamidoche M, et al Microstructured and Mechanical Investigation of WC-TiC-Co segmented Carbides associated by Conventional Powder Metallurgy [ J]International Journal of Engineering Research in africa.2019,45:1-14 "indicates that adding TiC, TaC, NbC refines WC grains, but relatively speaking, the resulting cemented carbide is not particularly dense; (5) the invention patent with the patent number of CN 112359241A adopts in-situ reaction to generate fine crystal WC powder, and further sinters the fine crystal WC powder with coarse crystal WC powder to generate bicrystal non-uniform hard alloy, so that the performance is improved while the production cost is reduced, but the in-situ reaction is difficult to control; (6) the selection of a proper process can have certain influence on the hard alloy, and particularly, the traditional one-step sintering method can not improve the compactness of a sintered sample while inhibiting the growth of crystal grains.
The WC hard alloy with single crystal grain size has poor comprehensive performance. The hard alloy containing the coarse crystal-fine crystal interweaved structure has the advantages that fine crystal grains can be filled in coarse crystal pores to improve the density and the hardness of the material, and the coarse crystal grains can effectively prevent cracks from expanding, increase the crack expansion stroke and improve the fracture toughness of the material, so that the hard alloy containing the coarse crystal-fine crystal interweaved structure has the advantages of high hardness and high wear resistance of the fine crystal grain hard alloy and high fracture toughness of the coarse crystal grain hard alloy, and the problem that the hard alloy containing the coarse crystal grains and the high toughness are difficult to exist simultaneously is solved. The invention patent with patent number CN 103667844 a proposes to prepare a hard alloy with non-uniform thickness structure, however, by blending and sintering WC powder with different thickness and different particle size and other powder raw materials, the toughness of the alloy can be improved to some extent, but the preparation cost of the ultra-fine WC is high, and in addition, the aggregation and non-uniform distribution of the thick and thin WC powder are easily generated during the sintering process, especially if the nano-grains are additionally mixed for co-sintering, the nano-grains are easily agglomerated, and the agglomerated grains may also affect the alloy performance.
The above mentioned aspects relate to several important fields of improving the hard alloy at present, but still have more or less problems, how to prepare the coarse crystal-fine crystal interweaved structure WC hard alloy on the basis of reducing the dosage of the Co powder binder, improve the comprehensive performance of the WC hard alloy, and urgently need new technology to overcome the difficulties.
Disclosure of Invention
The invention provides a multi-grain-size hard alloy and a preparation method thereof, aiming at the defects of the prior art, the special component structure of the amorphous alloy and the characteristic of precipitating nano-grains at high temperature are considered, a specific type of amorphous alloy phase is added into the traditional hard alloy, beneficial metal and compounds thereof are precipitated in the sintering process, a novel hard alloy containing multi-grain size is formed, the utilization rate of the added metal is ensured to be improved, Co is partially replaced, and the multi-aspect performance of the hard alloy is improved.
In order to achieve the purpose, the invention provides a preparation method of a hard alloy with multiple grain sizes, which comprises the following steps:
(1) fully mixing WC powder, Co powder, amorphous alloy powder and a forming agent according to a target alloy component proportion to obtain mixed powder; wherein the glass transition temperature of the amorphous alloy is lower than the melting point of WC;
(2) applying rectangular pulse current and constant current to the mixed powder, and applying sintering pressure to make the amorphous alloy powder and other powder in the mixed powder generate primary bonding within the temperature range of a supercooled liquid phase region, so that the mixed powder is presintered under the multi-field coupling action of an electric field, a magnetic field, a temperature field and a stress field;
(3) further applying rectangular pulse current and constant current to the pre-sintered sample obtained in the step (2), and applying sintering pressure to enable the sample to be subjected to densification sintering under the multi-field coupling action of an electric field, a magnetic field, a temperature field and a stress field, so that W-rich phase fine crystals are precipitated from the amorphous alloy, and the W-rich phase fine crystals and WC coarse crystals form hard alloy with a multi-grain scale;
the pre-sintering is superplastic hot-pressing sintering, the superplasticity of the amorphous alloy in a supercooled liquid region is utilized to realize primary bonding, and the amorphous alloy is used as a bonding phase to reduce the densification sintering time and avoid the growth of WC grains; the densification sintering is liquid phase sintering with Co as a binder phase, so that raw material powder is further bonded, W-rich nano crystals are crystallized and precipitated from the amorphous alloy, and beneficial elements or compounds thereof are introduced to form the hard alloy with the multi-grain size.
Preferably, the WC powder has a particle size of 0.5 to 1.5 μm, the Co powder has a particle size of 0.5 to 1.5 μm, and the amorphous alloy powder has a particle size of 0.1 to 0.5 μm.
In the mixed powder, the content of Co powder is 2-6 wt.%, the content of amorphous alloy powder is 3-10 wt.%, the content of forming agent is 0.2-0.5 wt.%, and the rest is WC powder; the forming agent is selected from paraffin, polyethylene glycol and rubber, can play a role in lubricating powder and a die, and reduces the friction force between the die and a material so as to ensure the uniformity of a pressed compact.
Preferably, the wetting angle of the amorphous alloy and the WC matrix is between 10 and 70 degrees, and the amorphous alloy is in a strong wetting state.
Preferably, the amorphous alloy contains one or more of W, C, Ni and Cu; the glass transition temperature of the amorphous alloy is 400-900 ℃.
Further preferably, the amorphous alloy further contains an element capable of inhibiting the growth of WC grains, and the element capable of inhibiting the growth of WC grains is preferably a transition metal element or a metal carbide thereof.
Further preferably, the amorphous alloy further contains a rare earth element or a rare earth compound capable of lowering the sintering temperature.
More preferably, the amorphous alloy further contains a metal element having a similar atomic radius to Co, preferably an iron group element such as Ni or Fe, and the metal element can replace Co, thereby reducing the amount of Co used.
Preferably, the amorphous alloy is a tungsten-based amorphous alloy.
Preferably, the amorphous alloy powder is prepared by adopting an atomization method or a mechanical alloying method.
Preferably, the step (1) adopts ball milling to fully mix various raw materials, and the technological parameters in the ball milling process are as follows: the ball milling speed is 120rpm-600rpm, the ball milling time is 24h-72h, the material of the grinding ball is stainless steel, and the ball material ratio is 30:1-3: 1.
Preferably, the pre-sintering process parameters in the step (2) include: the peak value, the base value, the frequency and the duty ratio of the rectangular pulse current are 2850A-3600A, 120A-360A, 50Hz and 45% -55%, the forming consolidation pressure is 10MPa-50MPa, the constant current is 800A-1000A, the heat preservation time is shorter than the minimum crystallization starting time when the amorphous alloy component is above the glass transition temperature, and the sintering temperature is controlled within a supercooled liquid phase region; and pre-sintered to less than 1 x 10-4Pa under vacuum or inert gas protection.
Preferably, the densification sintering temperature of the step (3) is controlled to be 1200-1400 ℃, and the sintering time is 5-7 min; preferably, the sintering is carried out for 1 minute under pulse current and for 4-6 minutes under constant current.
Preferably, the densification sintering process parameters in the step (3) comprise: the peak value, the base value, the frequency and the duty ratio of the rectangular pulse current are 2850A-3600A, 120A-360A, 50Hz and 45% -55%, the forming consolidation pressure is 10MPa-50MPa, the constant current is 1500A-2000A, and the range is less than 1 x 10-4Pa under vacuum or under inert gas protection.
According to another aspect of the invention, the polycrystalline grain size hard alloy prepared by the preparation method is provided.
Preferably, the cemented carbide comprises 2-6 wt.% Co, 3-10 wt.% amorphous alloy composition, 0.2-0.5 wt.% forming agent, balance WC; the hard alloy comprises micron-submicron-nanometer multi-scale structure WC crystal grains, wherein the micron is controlled to be 1-5 mu m, the submicron is controlled to be 0.1-1 mu m, and the nanometer particles are controlled to be 10-100 nm.
Generally, compared with the prior art, the above technical solution conceived by the present invention has the following beneficial effects:
(1) the invention provides a preparation method of a novel hard alloy with multiple grain sizes aiming at the characteristics of amorphous alloy. Compared with the traditional method of directly doping other phases in the WC-Co hard alloy, the method has the following obvious advantages: (a) in the pre-sintering process of the amorphous alloy in the supercooling liquid phase region, the superplasticity of the amorphous alloy is utilized to achieve the effect of primary bonding between the powder, promote the bonding and reduce the use of Co; (b) the amorphous alloy separates out a nanocrystalline phase in the sintering process to form a novel hard alloy containing a coarse crystal-fine crystal interweaving structure, and the toughness, hardness and wear resistance of the alloy can be obviously improved; (c) by regulating and controlling the components of the amorphous alloy, a plurality of beneficial elements can be simultaneously introduced into the hard alloy, crystal grains are refined, and the density of the alloy is improved; (d) other doping elements are introduced in the form of adding alloy, so that compared with directly doping elements, the burning loss can be obviously reduced, and the utilization rate of metal is improved. In addition, the invention can adjust the components of the amorphous alloy in time and realize the flexible design and preparation of the components of the hard alloy.
(2) The invention ball-mills and mixes tungsten-based amorphous alloy powder, cobalt powder, WC powder and a forming agent, firstly uses amorphous alloy as a binder in an amorphous alloy supercooled liquid region to preliminarily bind the powder, and then uses Co powder as the binder to carry out densification sintering at high temperature. Amorphous alloy in-situ crystallization precipitation of nano WC and W in densification sintering process2The introduction of the tungsten-based amorphous alloy powder is matched with a two-step sintering process, so that the WC hard alloy with a coarse crystal-fine crystal interweaved structure (preferably a micron-submicron-nanometer multi-scale structure) with excellent comprehensive performance can be prepared.
(3) Unlike the pre-sintering step in which amorphous alloy is used as the main binding phase, the densification sintering step of the invention uses Co as the main binding phase to provide the toughness of the hard alloy, and the amorphous alloy is used for crystallizing and separating out nano fine crystal particles to form an interwoven structure with WC coarse crystal particles, thereby improving the comprehensive performance of the hard alloy.
(4) The invention adopts a two-step multi-physical-field coupling rapid sintering technology to successfully prepare a novel hard alloy containing a coarse crystal-fine crystal interweaving structure, and therefore, the invention also provides a novel hard alloy component design and preparation method, in particular to a method for preparing the hard alloy by adopting two steps of pre-sintering and densification sintering on mixed powder by adopting proper process parameters and utilizing the two-step multi-physical-field coupling rapid sintering technology. Compared with the traditional sintering process, the method has the following obvious advantages: (a) by adopting a multi-field coupling rapid sintering technology of a temperature field, a pressure field, an electric field and a magnetic field, the sintering temperature can be reduced, the sintering time can be shortened, and the high-density hard alloy can be prepared; (b) through the pre-sintering, the time of densification sintering can be reduced, so that the growth of WC grains and the phase change of Co are inhibited, the porosity of the alloy is reduced, and the densification of the alloy is improved. Meanwhile, the densification sintering time is greatly reduced, so that the process time can be reduced, and the production cost is reduced. (c) The amorphous alloy is crystallized and precipitated with nanometer WC and W in the densification sintering process2C and other hard alloy phases, and beneficial elements or compounds thereof are introduced to form the hard alloy with a multi-grain size with the matrix phase WC coarse crystal; meanwhile, the compound formed by crystallization of the amorphous alloy element, such as CrC, can also inhibit the growth of WC coarse crystals and improve the comprehensive performance of the hard alloy.
Drawings
FIG. 1 is a flow chart of a novel cemented carbide containing a coarse grain-fine grain interlace structure and a method of making the same according to the present invention;
FIG. 2 is a diagram of a two-step multi-physical field coupling rapid sintering mechanism according to the present invention.
FIG. 3 is a manufacturing system used in some embodiments of the present invention to manufacture the novel cemented carbide of the present invention containing a coarse grain-fine grain microstructure.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Aiming at the problem of Co doping substitution faced by the traditional hard alloy and the requirement of improving the performance of the hard alloy at present, the invention provides a novel hard alloy with multiple grain sizes and a preparation method thereof, and the method can successfully prepare the hard alloy meeting the expected requirement of people by a two-step method multi-physical field coupling rapid sintering technology: the addition of the amorphous alloy can reduce the use of Co and improve the compactness of the hard alloy, and the toughness, hardness, wear resistance and corrosion resistance of the hard alloy can be properly improved by regulating and controlling the components of the amorphous alloy.
The preparation method of the hard alloy with multiple grain sizes, as shown in fig. 1 and 2, comprises the following steps:
(1) fully mixing WC powder, Co powder, amorphous alloy powder and a forming agent according to a target alloy component proportion to obtain mixed powder; wherein the glass transition temperature of the amorphous alloy is lower than the melting point of WC;
(2) applying rectangular pulse current and constant current to the mixed powder, and applying sintering pressure to make the amorphous alloy powder and other powder in the mixed powder generate primary bonding within the temperature range of a supercooled liquid phase region, so that the mixed powder is presintered under the multi-field coupling action of an electric field, a magnetic field, a temperature field and a stress field;
(3) and (3) further applying rectangular pulse current and constant current to the pre-sintered sample obtained in the step (2), and applying sintering pressure to enable the sample to be subjected to densification sintering under the multi-field coupling action of an electric field, a magnetic field, a temperature field and a stress field, so that the W-rich phase is separated out from the amorphous alloy, and the W-rich phase and WC coarse crystals form the hard alloy with a multi-grain size.
The invention provides a sintering method by coupling multiple physical fields by a two-step method, which comprises the following steps: firstly, pre-sintering in the temperature range of the supercooled liquid region of the amorphous alloy, then densifying and sintering, and improving the performance of the hard alloy by adding amorphous alloy powder for the first time: (1) the amorphous alloy supercooled liquid region is presintered, and the superplasticity of the amorphous alloy is utilized to achieve the effect of primary bonding so as to reduce the use of Co; (2) the components of the amorphous alloy powder are multiple, and a plurality of beneficial elements can be simultaneously introduced into the hard alloy by regulating and controlling the components of the amorphous alloy; (3) after preliminary bonding, the densification sintering time can be obviously reduced, and a phase containing WC crystal grains is precipitated to prevent WC from growing up, so that the density is improved: (4) in the densification sintering process, the amorphous alloy precipitates a W-rich phase, and can form a novel hard alloy containing a coarse crystal-fine crystal interweaving structure with WC coarse crystals, so that the toughness of the hard alloy is improved.
In order to obtain a new cemented carbide containing micro-sub-micron-nano multi-scale structures, as required by the intended target, in some embodiments the amorphous alloy is selected with the following criteria: the amorphous alloy is required to have good wettability with the WC matrix, for example, the wetting angle of the amorphous alloy and the WC matrix is preferably between 10 and 70 degrees; the glass transition temperature is 400-900 ℃ and is lower than the melting point of WC. The selection of the amorphous alloy composition can be carried out according to the following principle: (a) from the viewpoint of wettability, elements having excellent wettability with WC in amorphous alloys are generally selected, including W, C, Ni, Cu, and the like; (b) adding transition metal and its metal carbide, such as VC, Cr, into amorphous alloy3C2、TaC、NbC、Mo2C and the like, which can effectively inhibit the growth of WC crystal grains; (c) doping of amorphous alloys with rare-earth elements or rare-earth compounds, e.g. Y2O3、CeO2Y and the like, can effectively reduce the sintering temperature, refine crystal grains and improve the physical and chemical properties; (d) doping other metals, such as Al, B, Si, C and the like can also refine WC grains; (e) metal elements with the atomic radius similar to that of Co, including iron group elements such as Ni and Fe, are selected to play a role in replacing metal Co; (f) other specific component selection can adopt methods such as a theoretical criterion method, a high-throughput experiment method, an element substitution method, machine learning, neural network prediction and the like.
In a preferred embodiment, the amorphous alloy used in the present invention is a W-based amorphous alloy. Including but not limited to W30Fe38B22C10Amorphous alloy, W30Fe28Cr10B22C10Amorphous alloy, W46Ru37B17Amorphous alloy, W38Ir17Ru31B14Amorphous alloy, W54Rh26B20Amorphous alloy, W44Os40B16Amorphous alloy, W30Fe28.2Cr9.8B22C10Amorphous alloy, W17.9Ni65.6B13.5V3Amorphous alloys, and the like.
The glass transition temperature of the amorphous alloy selected by the invention is required to be ensured to be 400-900 ℃, the glass transition temperature of the amorphous alloy is required to be lower than the densification sintering temperature of 1200-1500 ℃, and the difference value between the glass transition temperature of the amorphous alloy and the densification sintering temperature is required to be larger than 300 ℃.
In the step (1) of the invention, micron-sized alloy raw material powder can be obtained by adopting a powder preparation technology. In some embodiments, in the step (1), the amorphous alloy is prepared into the alloy raw material powder with the grain size of micron-scale or nanometer-scale by using atomization powder preparation method, mechanical alloying method and other processes.
In the step (2) of the invention, WC, Co, amorphous alloy powder and a forming agent can be uniformly mixed by adopting various powder mixing methods. In some embodiments, step (2) uses a ball milling process to mix the raw material powders uniformly. The technological parameters of the ball milling process are as follows: the ball milling speed is 120rpm-600rpm, the ball milling time is 24h-72h, the material of the grinding ball is stainless steel, and the ball material ratio is 30:1-3: 1.
The invention relates to a multi-grain-size hard alloy, which is an alloy system prepared by taking Co powder, WC powder, forming agent powder and amorphous alloy powder as raw materials and adopting a two-step multi-physical-field coupling rapid sintering technology.
In some embodiments of the present invention, a system as shown in fig. 3 is used to prepare a multi-grain-scale cemented carbide, the mixed powder of amorphous alloy powder, tungsten carbide powder, cobalt powder and a forming agent is placed in a powder sintering device, a pressure system of the powder sintering device is used to apply sintering, forming and consolidation pressure to a powder sample, a direct current pulse constant current generator is used to apply rectangular pulse current to the sample, an axial magnetic field is applied to the powder sample through coil electrification, and the powder sample is sequentially presintering and densifying sintering under the given process parameters to prepare the multi-grain-scale cemented carbide of the present invention.
By adopting the component design and preparation method, the components and the performance of the hard alloy are improved by adding the amorphous alloy and the two-step method rapid sintering process, and compared with the traditional method of directly doping other phases in the WC-Co alloy, the method has the following obvious advantages: (a) in the pre-sintering process of the amorphous alloy in the supercooling liquid phase region, the superplasticity of the amorphous alloy is utilized to achieve the effect of primary bonding between the powder, promote the bonding and reduce the use of Co; (b) the amorphous alloy separates out a nanocrystalline phase in the sintering process to form a novel hard alloy containing a coarse crystal-fine crystal interweaving structure, and the toughness, hardness and wear resistance of the alloy can be obviously improved; (c) by regulating and controlling the components of the amorphous alloy, a plurality of beneficial elements can be simultaneously introduced into the hard alloy, crystal grains are refined, and the density of the alloy is improved; (d) other doping elements are introduced in the form of adding alloy, so that compared with directly doping elements, the burning loss can be obviously reduced, and the utilization rate of metal is improved. In addition, the invention can realize flexible design and preparation of the hard alloy components even if the components of the amorphous alloy are adjusted.
On the other hand, the invention can successfully prepare the hard alloy with multiple grain sizes by adopting a two-step multi-physical-field coupling rapid sintering technology, so the invention also provides a novel hard alloy component design and preparation method, and particularly adopts proper process parameters and the two-step multi-physical-field coupling rapid sintering technology to prepare the hard alloy by adopting two steps of pre-sintering and densification sintering on mixed powder. Compared with the traditional sintering process, the method has the following obvious advantages: (a) by adopting a multi-field coupling rapid sintering technology of a temperature field, a pressure field, an electric field and a magnetic field, the sintering temperature can be reduced, the sintering time can be shortened, and the high-density hard alloy can be prepared; (b) through the pre-sintering, the time of densification sintering can be reduced, so that the growth of WC grains and the phase change of Co are inhibited, the porosity of the alloy is reduced, and the densification of the alloy is improved. Meanwhile, the densification sintering time is greatly reduced, so that the process time can be reduced, and the production cost is reduced.
Aiming at the application requirements of novel hard alloy and the problems to be solved, the invention provides a novel design method and a preparation method of a novel hard alloy component containing a micron-submicron-nanometer multi-scale structure. The method comprises the steps of firstly, preferably selecting amorphous alloy meeting expected requirements, preparing Co powder, WC powder and amorphous alloy powder with the particle size of micron or nanometer, weighing raw material powder and a forming agent according to the proportion of target alloy components, and obtaining the high-density novel hard alloy through a two-step multi-physical field coupling rapid sintering technology after ball milling and mixing uniformly. By designing the components of the amorphous alloy and innovating the preparation process, the use of Co can be reduced, the density of the alloy can be improved, and the mechanical property can be improved while the burning loss of the added elements is reduced.
The following are examples:
example 1
W is preferably selected from developed amorphous alloy composition library30Fe38B22C10And (3) amorphous alloy. (1) The glass transition temperature (T) of the amorphous alloyg) 985K, crystallization onset temperature (T)x) 1003K and 18K of supercooled liquid region; (2) the amorphous alloy contains W, C and other metal elements with better WC wettability; (3) the atomic radius of Fe and Co in the amorphous alloy is similar, the density, melting point, physical and chemical properties and the wettability to WC phase are all very similar, and the amorphous alloy can be doped with metal to replace Co and has the function of bonding; (4) the existence of B and C in the amorphous alloy can inhibit WC grains from aggregating and growing, weaken the WC dissolution and precipitation process and promote the refinement of alloy grains. Therefore, W is preferably selected30Fe38B22C10The amorphous alloy is used as the additive phase of the WC-Co hard alloy.
Weighing metal raw materials according to nominal components, wherein the content of Co powder is 8 wt.%, the content of amorphous alloy powder is 7 wt.%, the content of forming agent polyethylene glycol is 0.2 wt.%, and preparing and screening the metal raw material powder by an atomization powder preparation method, wherein the particle size of WC powder is 0.5-1.5 μm, the particle size of Co powder is 0.5-1.5 μm, and the particle size of W powder is 0.5-1.5 μm30Fe38B22C10The grain diameter of the amorphous alloy powder is 0.1-0.5 μm, and the specific technological parameters are as follows: the alloy superheat degree is 50-100 ℃, the alloy is repeatedly smelted for five times to obtain a master alloy ingot, the high-purity argon atomization pressure is 3.5MPa, and the diameter of the diversion hole is 2 mm.
And uniformly mixing the original alloy powder and the forming agent by adopting a ball milling process to obtain mixed powder. The ball milling process parameters are as follows: the ball milling speed is 300rpm, the ball milling time is 72 hours, the material of the grinding ball is stainless steel, and the ball material ratio is 30: 1.
A two-step method multi-physical field coupling rapid sintering technology is adopted to prepare a novel hard alloy containing a micron-submicron-nanometer multi-scale structure. Firstly, presintering is adopted to enable the amorphous alloy to achieve the primary bonding effect in a supercooling liquid phase region. The technological parameters in the pre-sintering stage are as follows: the peak value, the base value, the frequency and the duty ratio of the rectangular pulse current are 2850A, 240A, 50Hz and 55%, the forming consolidation pressure is 30MPa, the constant current is 1000A, the sintering temperature is controlled to be 1000K, the sintering time is 4min, the pulse current is 1min + the constant current is 3min, and the frequency is less than 1 multiplied by 10-4Pa under vacuum or inert gas protection. The densification sintering process parameters are as follows: the peak value, the base value, the frequency and the duty ratio of the rectangular pulse current are 3600A, 360A, 50Hz and 55 percent respectively, the forming consolidation pressure is 30MPa, the constant current is 1500A, the sintering time is 7min, the pulse current is 1min and the constant current is 6min, the sintering temperature is controlled to be 1400K and is less than 1 multiplied by 10-4Pa under vacuum or under inert gas protection.
The novel hard alloy containing the micron-submicron-nanometer multi-scale structure can be prepared by the process.
Example 2
W is preferably selected from developed amorphous alloy composition library30Fe28Cr10B22C10And (3) amorphous alloy. (1) The crystallization initiation temperature (T) of the amorphous alloyx) Is 1003K; (2) the amorphous alloy contains W, C and other metal elements with better WC wettability; (3) the atomic radii of Fe and Co in the amorphous alloy are similar, the density, melting point, physical and chemical properties and the wettability to WC phase are all very similar, and doping can be performedThe metal substitutes for Co, and plays a role in bonding; (4) the existence of B and C in the amorphous alloy can inhibit WC grains from aggregating and growing, weaken the WC dissolution and precipitation process and promote the refinement of alloy grains; (5) the presence of an appropriate amount of Cr in the amorphous alloy suppresses the size of WC grains. Therefore, W is preferably selected30Fe28Cr10B22C10The amorphous alloy is used as the additive phase of the WC-Co hard alloy.
Weighing metal raw materials according to nominal components, wherein the content of Co powder is 5 wt.%, the content of amorphous alloy powder is 10 wt.%, the content of forming agent styrene-butadiene-styrene rubber is 0.2 wt.%, and the metal raw material powder is prepared and screened by an atomization powder preparation method, wherein the particle size of WC powder is 0.5-1.5 μm, the particle size of Co powder is 0.5-1.5 μm, and the particle size of W powder is 0.5-1.5 μm30Fe28Cr10B22C10The grain diameter of the amorphous alloy powder is 0.1-0.5 μm, and the specific technological parameters are as follows: the alloy superheat degree is 50-100 ℃, the alloy is repeatedly smelted for five times to obtain a master alloy ingot, the high-purity argon atomization pressure is 3.5MPa, and the diameter of the diversion hole is 2 mm.
And uniformly mixing the original alloy powder and the forming agent by adopting a ball milling process to obtain mixed powder. The ball milling process parameters are as follows: the ball milling speed is 300rpm, the ball milling time is 72 hours, the material of the grinding ball is stainless steel, and the ball material ratio is 30: 1.
A two-step method multi-physical field coupling rapid sintering technology is adopted to prepare a novel hard alloy containing a micron-submicron-nanometer multi-scale structure. Firstly, presintering is adopted to enable the amorphous alloy to achieve the primary bonding effect in a supercooling liquid phase region. The technological parameters in the pre-sintering stage are as follows: the peak value, the base value, the frequency and the duty ratio of the rectangular pulse current are 2850A, 240A, 50Hz and 55%, the forming consolidation pressure is 30MPa, the constant current is 1000A, the sintering temperature is controlled to be 1000K, the sintering time is 4min, the pulse current is 1min + the constant current is 3min, and the frequency is less than 1 multiplied by 10-4Pa under vacuum or inert gas protection. The densification sintering process parameters are as follows: the peak value, the base value, the frequency and the duty ratio of the rectangular pulse current are 3600A, 360A, 50Hz and 55 percent respectively, the forming consolidation pressure is 30MPa, the constant current is 1500A, the sintering time is 7min, the pulse current is 1min + the constant current is 6min, and the sintering temperature is ensuredControlling at 1400K and less than 1 × 10-4Pa under vacuum or under inert gas protection.
The novel hard alloy containing the micron-submicron-nanometer multi-scale structure can be prepared by the process.
Example 3
W is preferably selected from developed amorphous alloy composition library46Ru37B17And (3) amorphous alloy. (1) The glass transition temperature (T) of the amorphous alloyg) At 1149K, crystallization initiation temperature (T)x) 1174K, supercooled liquid region 25K; (2) the amorphous alloy contains metal elements with good wettability of W and WC; (3) the existence of B in the amorphous alloy can inhibit WC grains from aggregating and growing, weaken the WC dissolution and precipitation process and promote the refinement of alloy grains; . Therefore, W is preferably selected46Ru37B17The amorphous alloy is used as the additive phase of the WC-Co hard alloy.
Weighing metal raw materials according to nominal components, wherein the content of Co powder is 5 wt.%, the content of amorphous alloy powder is 10 wt.%, the content of forming agent paraffin is 0.2 wt.%, and preparing and screening the metal raw material powder by an atomization powder preparation method, wherein the grain diameter of WC powder is 0.5-1.5 μm, the grain diameter of Co powder is 0.5-1.5 μm, and the grain diameter of W powder is 0.5-1.5 μm46Ru37B17The grain diameter of the amorphous alloy powder is 0.1-0.5 μm, and the specific technological parameters are as follows: the alloy superheat degree is 50-100 ℃, the alloy is repeatedly smelted for five times to obtain a master alloy ingot, the high-purity argon atomization pressure is 3.5MPa, and the diameter of the diversion hole is 2 mm.
And uniformly mixing the original alloy powder and the forming agent by adopting a ball milling process to obtain mixed powder. The ball milling process parameters are as follows: the ball milling speed is 300rpm, the ball milling time is 72 hours, the material of the grinding ball is stainless steel, and the ball material ratio is 30: 1.
A two-step method multi-physical field coupling rapid sintering technology is adopted to prepare a novel hard alloy containing a micron-submicron-nanometer multi-scale structure. Firstly, presintering is adopted to enable the amorphous alloy to achieve the primary bonding effect in a supercooling liquid phase region. The technological parameters in the pre-sintering stage are as follows: the peak value, the base value, the frequency and the duty ratio of the rectangular pulse current are 2850A, 240A, 50Hz and 55 percent respectively, the forming consolidation pressure is 30MPa, and the constant current is constant1000A, ensuring that the sintering temperature is controlled at 1160K, the sintering time is 5min, the pulse current is 1min + the constant current is 4min, and the sintering temperature is less than 1 × 10-4Pa under vacuum or inert gas protection. The densification sintering process parameters are as follows: the peak value, the base value, the frequency and the duty ratio of the rectangular pulse current are 3600A, 360A, 50Hz and 55 percent respectively, the forming consolidation pressure is 30MPa, the constant current is 1500A, the sintering time is 7min, the pulse current is 1min and the constant current is 6min, the sintering temperature is controlled to be 1400K and is less than 1 multiplied by 10-4Pa under vacuum or under inert gas protection.
The novel hard alloy containing the micron-submicron-nanometer multi-scale structure can be prepared by the process.
According to the invention, the amorphous alloy is used as a binder, the pre-sintering temperature is reduced, meanwhile, various beneficial alloy elements are introduced in an alloy form, the burning loss is avoided, and the use of Co can be effectively reduced while the wettability with a matrix is ensured; by regulating and controlling the components of the amorphous alloy, a series of purposes of reducing sintering temperature, refining crystal grains, improving density, improving mechanical property and the like are achieved; the invention reduces the time required by high-temperature sintering, refines crystal grains and further improves the density of the alloy by a two-step multi-physical field coupling rapid sintering technology. Therefore, the invention can reduce the use of Co content in the traditional WC-Co hard alloy, improve the compactness, improve the mechanical property of the alloy, reduce the process time and reduce the cost.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The preparation method of the hard alloy with the multi-grain size is characterized by comprising the following steps of:
(1) fully mixing WC powder, Co powder, amorphous alloy powder and a forming agent according to a target alloy component proportion to obtain mixed powder; wherein the glass transition temperature of the amorphous alloy is lower than the melting point of WC;
(2) applying rectangular pulse current and constant current to the mixed powder, and applying sintering pressure to make the amorphous alloy powder and other powder in the mixed powder generate primary bonding within the temperature range of a supercooled liquid phase region, so that the mixed powder is presintered under the multi-field coupling action of an electric field, a magnetic field, a temperature field and a stress field;
(3) further applying rectangular pulse current and constant current to the pre-sintered sample obtained in the step (2), and applying sintering pressure to enable the sample to be subjected to densification sintering under the multi-field coupling action of an electric field, a magnetic field, a temperature field and a stress field, so that W-rich phase fine crystals are precipitated from the amorphous alloy, and the W-rich phase fine crystals and WC coarse crystals form hard alloy with a multi-grain scale;
the pre-sintering is superplastic hot-pressing sintering, the superplasticity of the amorphous alloy in a supercooled liquid region is utilized to realize primary bonding, and the amorphous alloy is used as a bonding phase to reduce the densification sintering time and avoid the growth of WC grains; the densification sintering is liquid phase sintering with Co as a binder phase, so that raw material powder is further bonded, W-rich nano crystals are crystallized and precipitated from the amorphous alloy, and beneficial elements or compounds thereof are introduced to form the hard alloy with the multi-grain size.
2. The method according to claim 1, wherein the WC powder has a particle size of 0.5 μm to 1.5 μm, the Co powder has a particle size of 0.5 μm to 1.5 μm, and the amorphous alloy powder has a particle size of 0.1 μm to 0.5 μm;
in the mixed powder, the content of Co powder is 2-6 wt.%, the content of amorphous alloy powder is 3-10 wt.%, the content of forming agent is 0.2-0.5 wt.%, and the balance is WC powder; the forming agent is selected from paraffin, polyethylene glycol and rubber.
3. The method according to claim 1, wherein the wetting angle of the amorphous alloy with the WC substrate is between 10 and 70 degrees, and the amorphous alloy is in a strongly wetted state.
4. The method according to claim 1, wherein the amorphous alloy contains one or more of W, C, Ni, and Cu; the glass transition temperature of the amorphous alloy is 400-900 ℃.
5. The method according to claim 1, wherein the amorphous alloy further contains an element capable of suppressing WC grain growth, and the element capable of suppressing WC grain growth is a transition metal element or a metal carbide thereof;
further preferably, the amorphous alloy further contains a rare earth element or a rare earth compound capable of reducing the sintering temperature;
more preferably, the amorphous alloy further contains a metal element having a similar atomic radius to Co, preferably an iron group element such as Ni or Fe, and the metal element can replace Co, thereby reducing the amount of Co used.
6. The method according to claim 1, wherein the amorphous alloy is a tungsten-based amorphous alloy.
7. The method of claim 1, wherein the pre-sintering process parameters of step (2) comprise: the peak value, the base value, the frequency and the duty ratio of the rectangular pulse current are 2850A-3600A, 120A-360A, 50Hz and 45% -55%, the forming consolidation pressure is 10MPa-50MPa, the constant current is 800A-1000A, the heat preservation time is shorter than the minimum crystallization starting time when the amorphous alloy component is above the glass transition temperature, and the sintering temperature is controlled within a supercooled liquid phase region; and pre-sintered to less than 1 x 10-4Pa under vacuum or inert gas protection.
8. The preparation method of claim 1, wherein the densification sintering temperature in the step (3) is controlled to be 1200-1400 ℃, and the sintering time is 5-7 min;
the densification sintering process parameters in the step (3) comprise: the peak value, the base value, the frequency and the duty ratio of the rectangular pulse current are 2850A-3600A,120A-360A, 50Hz and 45% -55%, forming and consolidating pressure is 10MPa-50MPa, constant flow is 1500A-2000A, and the pressure is less than 1 × 10-4Pa under vacuum or under inert gas protection.
9. The multi-grain-size cemented carbide produced by the production method according to any one of claims 1 to 8.
10. The cemented carbide of claim 9, comprising 2-6 wt.% Co, 3-10 wt.% amorphous alloy constituents, 0.2-0.5 wt.% forming agent, balance WC; the hard alloy comprises micron-submicron-nanometer multi-scale structure WC crystal grains, wherein the micron is controlled to be 1-5 mu m, the submicron is controlled to be 0.1-1 mu m, and the nanometer particles are controlled to be 10-100 nm.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114346237A (en) * | 2021-12-11 | 2022-04-15 | 深圳大学 | Application of amorphous alloy, composite material and preparation method thereof |
| CN115286391A (en) * | 2022-07-26 | 2022-11-04 | 广东正信硬质材料技术研发有限公司 | Binder-free hard alloy material and preparation method thereof |
| CN115821092A (en) * | 2022-11-22 | 2023-03-21 | 华中科技大学 | Preparation method of hard alloy composite material with gradient structure and performance |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3647401A (en) * | 1969-06-04 | 1972-03-07 | Du Pont | Anisodimensional tungsten carbide platelets bonded with cobalt |
| CN111705234A (en) * | 2020-07-22 | 2020-09-25 | 东莞颠覆产品设计有限公司 | Preparation process of high-hardness product |
| CN111804889A (en) * | 2020-07-22 | 2020-10-23 | 东莞颠覆产品设计有限公司 | Preparation process of composite material |
-
2021
- 2021-06-04 CN CN202110627423.6A patent/CN113502426B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3647401A (en) * | 1969-06-04 | 1972-03-07 | Du Pont | Anisodimensional tungsten carbide platelets bonded with cobalt |
| CN111705234A (en) * | 2020-07-22 | 2020-09-25 | 东莞颠覆产品设计有限公司 | Preparation process of high-hardness product |
| CN111804889A (en) * | 2020-07-22 | 2020-10-23 | 东莞颠覆产品设计有限公司 | Preparation process of composite material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114346237A (en) * | 2021-12-11 | 2022-04-15 | 深圳大学 | Application of amorphous alloy, composite material and preparation method thereof |
| CN114346237B (en) * | 2021-12-11 | 2023-07-11 | 深圳大学 | Application of amorphous alloy, composite material and preparation method thereof |
| CN115286391A (en) * | 2022-07-26 | 2022-11-04 | 广东正信硬质材料技术研发有限公司 | Binder-free hard alloy material and preparation method thereof |
| CN115821092A (en) * | 2022-11-22 | 2023-03-21 | 华中科技大学 | Preparation method of hard alloy composite material with gradient structure and performance |
| CN115821092B (en) * | 2022-11-22 | 2023-12-26 | 华中科技大学 | Preparation method of hard alloy composite material with gradient structure and performance |
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