CN114752801A - Plate-shaped crystal reinforced net-shaped structure hard alloy and preparation method thereof - Google Patents
Plate-shaped crystal reinforced net-shaped structure hard alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a plate-shaped crystal reinforced net-shaped structure hard alloy and a preparation method thereof. In order to solve the problems of poor alloy high-temperature performance, insufficient corrosion resistance, insufficient service life of alloy and the like in the prior art, the invention provides a preparation method of a plate-shaped crystal reinforced hard alloy with a net-shaped structure. The plate-shaped crystal reinforced net-shaped structure hard alloy prepared by the method has high hardness and toughness, and is widely applied to various fields of engineering machinery, machining, aerospace and the like.
Description
Technical Field
The invention belongs to the field of powder metallurgy, and particularly relates to a plate-shaped crystal reinforced net-shaped structure hard alloy and a preparation method thereof.
Background
The hard alloy is an alloy prepared by using powder of one or more refractory carbides (tungsten carbide, titanium carbide, etc.) as a main component, adding metal powder (cobalt, nickel, etc.) as a binder, and performing a powder metallurgy method. The hard alloy has a series of excellent performances of high hardness, wear resistance, good strength and toughness, heat resistance, corrosion resistance and the like, particularly high hardness and wear resistance, basically keeps unchanged even at a temperature of 500 ℃, and still has high hardness at 1000 ℃. The hard alloy is widely used as a cutter material, such as a turning tool, a milling cutter, a plane cutter, a drill bit, a boring cutter and the like, is used for cutting cast iron, nonferrous metals, plastics, chemical fibers, graphite, glass, stones and common steel, and can also be used for cutting refractory steel, stainless steel, high manganese steel, tool steel and other materials which are difficult to process. In addition, because of its high hardness and toughness, cemented carbide is widely used in various fields such as engineering machinery, machining, aerospace, and the like. However, with the development of science and technology and the complexity of engineering working conditions, people have made higher requirements on the performance of cemented carbide, and have required higher hardness and toughness.
The hardness (wear resistance) and toughness (impact and fracture resistance) of the hard alloy are the most critical performance indexes, and determine the service efficiency and service life of the product. In the process of using the hard alloy, people hope to obtain better wear resistance and simultaneously the toughness can not be reduced, and the hard alloy structure with a normal structure can hardly meet the requirement. Because the common hard alloy belongs to a brittle material, the hardness and the toughness of the common hard alloy cannot be considered at the same time. In order to obtain the 'double-high' hard alloy, which is suitable for the use requirement of actual working conditions, after the superfine hard alloy, the coarse-grain hard alloy, the mixed-grain hard alloy, the gradient hard alloy and the plate-shaped grain hard alloy are developed successively, the American Smith oilfield service International corporation 1999 discloses the reticulate hard alloy, the high-hardness core tissue of the alloy provides high wear resistance, the high-toughness aggregate plays the roles of passivating cracks, deflecting cracks and absorbing impact energy, and the impact fracture resistance is enhanced, so that the comprehensive mechanical property with high wear resistance and high toughness is obtained.
The hard alloy with a net structure is a new-structure hard alloy developed in recent 20 years, and is considered to be the most potential hard alloy for mining due to high hardness and high impact toughness. The hard alloy with the net-shaped structure is a hard alloy with a novel structure, wherein a high-hardness composite material is used as a core tissue, a high-toughness metal, an alloy material or a composite material is used as a matrix tissue, and the core tissue is refined by a powder metallurgy method and is uniformly distributed in the matrix tissue. The service life of the net-shaped alloy can be prolonged by more than 15% due to the excellent comprehensive mechanical property of the net-shaped alloy.
The hard alloy with the net structure has high wear resistance and high impact toughness, is a mine hard alloy with development potential in the future, and has been subjected to a great deal of research by the majority of scientific researchers. For example, patent CN106191498A discloses a method for preparing a hard alloy with a net structure, which can effectively solve the problem that the existing coarse cobalt crystals and fine cobalt crystals are difficult to mix uniformly. The preparation method comprises the following steps: A. granulating the low-cobalt fine-grain hard alloy mixture; B. preparing a mixture of high-cobalt coarse crystals into a suspension solution; C. b, placing the low-cobalt fine-grain mixed material grains prepared in the step A into a roller to roll, and spraying the high-cobalt coarse-grain suspension solution prepared in the step B onto the low-cobalt fine-grain mixed material grains while rolling, so that the low-cobalt fine-grain mixed material grains are uniformly wrapped by the high-cobalt coarse-grain mixed material; D. and C, pressing and sintering the mixed material particles prepared in the step C to prepare a finished product. The high-cobalt coarse-crystal mixture suspension solution is sprayed on the particles when the low-cobalt fine-crystal mixture rolls in the roller, and the low-cobalt fine-crystal mixture suspension solution is sprayed on the particles when the low-cobalt fine-crystal mixture rolls, so that the high-cobalt coarse-crystal mixture uniformly wraps the low-cobalt fine crystals. However, the method is still complicated, and the service life of the net-shaped alloy still needs to be further improved.
Moreover, as the preparation technology of the reticular alloy is not mature, the preparation process is longer, the cost is higher, and the prepared reticular structure hard alloy product generally has the problems of poor stability, overproof pore defects, poor appearance quality and the like. And the net-shaped alloy is ineffective due to continuous high temperature and acid corrosion when the rock drilling operation is carried out, so that the service life of the alloy is short.
The present invention is directed to solving, at least in part, one of the technical problems in the related art. Therefore, the invention aims to provide the hard alloy and the preparation method thereof, and the hard alloy with the plate-shaped crystal reinforced reticular structure prepared by the method solves the problems of poor high-temperature performance and insufficient corrosion resistance of the alloy, greatly prolongs the service life of the alloy and solves the problem of insufficient service life of the alloy.
Disclosure of Invention
The invention provides a preparation method of a plate-shaped crystal reinforced hard alloy with a reticular structure, aiming at solving the problems of poor alloy high-temperature performance, insufficient corrosion resistance, insufficient service life of alloy and the like in the prior art. According to the method, the plate-shaped crystal WC is introduced into the hard alloy with the reticular structure, and the high-temperature fatigue resistance and the corrosion resistance of the plate-shaped crystal are fully utilized, so that the reticular hard alloy has stable high-temperature performance and corrosion resistance besides the double-high performance, and the service life of the alloy is greatly prolonged.
In one aspect of the present invention, the present invention provides a method for preparing a plate-shaped crystal WC-reinforced cemented carbide with a mesh structure, comprising the following steps:
step 1: stirring and mixing soluble tungsten salt and soluble yttrium salt in a solvent to obtain a homogeneous solution, and carrying out spray drying on the solution to obtain precursor powder;
and 2, step: carrying out heat treatment on the precursor powder to obtain Y-containing tungsten powder;
and 3, step 3: carrying out ball milling and mixing on Y-containing tungsten powder, tungsten carbide, carbon black and cobalt powder, and carrying out vacuum drying after ball milling is finished to obtain a mixture;
and 4, step 4: and pressing and sintering the mixture to finally obtain the plate-shaped crystal reinforced reticular hard alloy.
Further, the mass ratio of W in the soluble tungsten salt to Y in the soluble yttrium salt in the step 1 is (3200-;
further, in the step 1, the soluble tungsten salt is ammonium metatungstate; in the step 1, the soluble yttrium salt is yttrium acetate; the solvent in the step 1 is pure water or a solvent.
Further, the heat treatment in step 2 is performed in a tube sintering furnace.
Further, in the step 2, the heat treatment is sintering under the action of hydrogen to obtain W powder with uniformly distributed Y elements.
Further, the heat treatment process in the step 2 is as follows: heating to 300-350 ℃, keeping the temperature for 0.5-2 h, continuously heating to 1000-1100 ℃, and keeping the temperature for 3.0-6.0 h.
Further, the mass ratio of the tungsten powder containing Y, the tungsten carbide, the carbon black and the cobalt powder in the step 3 is (50-55): (32-38): (3.3-3.7): (8-12).
Further, 2% of paraffin is added as a forming agent in the step 3, and the solid-liquid ratio is 2: 1, taking alcohol as a ball milling medium;
further, in the step 3, the rotation speed of the ball milling process is 260-300 r/min, the ball milling time is 24-48 h, and the ball-to-material ratio is (4.5-5.5): 1.
further, the grinding balls for ball milling the mixed materials in the step 3 are composed of YG8 hard alloy balls with two diameters of 3-5mm and 7-9mm, and the mass ratio of the two balls is 1: (3-4).
Further, in the step 3, the vacuum drying temperature is 80-110 ℃, and the drying time is 0.5-3 h;
further, in the step 4, the pressing pressure is 280-420 MPa, and the pressure maintaining time is 15-20 s.
Further, the sintering in the step 4 is carried out in a degreasing sintering high-pressure furnace, the temperature of the sintering is increased to 1430-1480 ℃ at the temperature rising rate of 6-12 ℃, the temperature is kept for 0.5-2.0 h, and the sintering pressure is 1.0-8.0 MPa.
In another aspect of the invention, the invention provides a plate-shaped crystal WC reinforced net-shaped structure hard alloy material, and the hard alloy is prepared by the method.
In another aspect of the invention, the invention also provides a plate-shaped crystal reinforced net-shaped structure hard alloy, the plate-shaped crystal WC is introduced into the net-shaped structure hard alloy, and the high-temperature fatigue resistance and corrosion resistance of the plate-shaped crystal are fully utilized, so that the net-shaped hard alloy has stable high-temperature performance and corrosion resistance besides the double high performance, and the service life of the alloy is greatly prolonged.
The invention has the beneficial effects that:
1. according to the invention, the plate-shaped crystal and the net structure are combined, and the prepared plate-shaped crystal reinforced net structure hard alloy has high toughness and hardness, and also has stable high-temperature performance and corrosion resistance, so that the service life of the alloy is greatly prolonged;
2. according to the invention, the soluble tungsten salt and the soluble yttrium salt are used for spray granulation and heat treatment to obtain the W powder with uniformly distributed Y element, so that the problems of small addition amount of the Y element and difficulty in uniform dispersion are avoided. According to the invention, through spray granulation and heat treatment, a very small amount of Y element can be added, so that a good uniform distribution effect can be achieved, and the service life of the alloy is prolonged to the maximum extent.
Drawings
To facilitate understanding by those skilled in the art, the invention is further described below with reference to the accompanying drawings.
FIG. 1 is a metallographic photograph of cemented carbide with a plate-like grain-reinforced network structure prepared in example 1.
FIG. 2 is an SEM photograph of the plate-shaped crystal reinforced network-structured cemented carbide prepared in example 1.
Detailed Description
The present invention will be further described in order to more clearly understand the objects, technical solutions and advantages of the present invention, but the scope of the present invention is not limited to the following examples, which are only used for describing the present invention in detail and are not limited in any way. The instruments and devices referred to in the following examples are conventional instruments and devices unless otherwise specified; the raw materials are all conventional commercial industrial raw materials unless otherwise specified; the related processing and manufacturing methods are all conventional methods unless otherwise specified. It is to be understood that these descriptions are only illustrative and are not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
In order to solve the problems of poor alloy high-temperature performance, insufficient corrosion resistance, insufficient service life of alloy and the like in the prior art, the invention provides a preparation method of a plate-shaped crystal reinforced net-shaped structure hard alloy.
In one aspect of the present invention, the present invention provides a method for preparing a plate-shaped crystal WC-reinforced cemented carbide with a mesh structure, comprising the following steps:
step 1: stirring and mixing soluble tungsten salt and soluble yttrium salt in a solvent to obtain a homogeneous solution, and carrying out spray drying on the solution to obtain precursor powder;
and 2, step: carrying out heat treatment on the precursor powder to obtain Y-containing tungsten powder;
and 3, step 3: carrying out ball milling and mixing on Y-containing tungsten powder, tungsten carbide, carbon black and cobalt powder, and carrying out vacuum drying after ball milling is finished to obtain a mixture;
and 4, step 4: and pressing and sintering the mixture to finally obtain the plate-shaped crystal reinforced reticular hard alloy.
Further, in the embodiment of the present invention, the mass ratio of W in the soluble tungsten salt to Y in the soluble yttrium salt in step 1 is (3200-. According to the invention, the W powder with uniformly distributed Y element is obtained by carrying out spray granulation and heat treatment on the soluble tungsten salt and the soluble yttrium salt, so that the problems of small addition amount of the Y element and difficulty in uniform dispersion are avoided. According to the invention, through spray granulation and heat treatment, a very small amount of Y element can be added, so that a good uniform distribution effect can be achieved, and the service life of the alloy is prolonged to the maximum extent.
Further, in an embodiment of the present invention, the soluble tungsten salt in step 1 is ammonium metatungstate; in the step 1, the soluble yttrium salt is yttrium acetate; the solvent in step 1 is pure water. However, the present invention is not limited to the above soluble tungsten salt, soluble yttrium salt, and solvent, and any other soluble tungsten salt, soluble yttrium salt, and solvent may be commercially available or homemade as known to those skilled in the art.
Further, in the embodiment of the present invention, the heat treatment in step 2 is performed in a tube sintering furnace; the tubular sintering furnace adopted by the invention can realize temperature-controllable sectional roasting and can at least bear the high temperature of more than 1200 ℃; the tube sintering furnace of the present invention is not particularly limited, and any commercially available or self-made tube sintering furnace known to those skilled in the art may be used.
Further, in the embodiment of the present invention, the heat treatment in step 2 is sintering under the action of hydrogen to obtain W powder in which Y element is uniformly distributed. The hydrogen gas used in the present invention is not particularly limited, and commercially available or self-made hydrogen gas known to those skilled in the art may be used.
Further, in the embodiment of the present invention, the heat treatment process in step 2 is: heating to 300-350 ℃, keeping the temperature for 0.5-2 h, continuously heating to 1000-1100 ℃, and keeping the temperature for 3.0-6.0 h. The method has the advantages that the heating program roasting is arranged in sections, so that the material can be heated more uniformly, the cracking conversion of the ammonium metatungstate at a low temperature is facilitated, and the uniform distribution of Y salt is facilitated. The inventor researches and finds that the plate-shaped crystal WC reinforced network structure hard alloy is easier to prepare in the reasonable temperature and time range. If the heat treatment temperature is too low, the heat treatment effect is poor, and the situation of insufficient and incomplete heat treatment is easy to occur; if the heat treatment temperature is too high, solid-phase agglomeration is liable to be formed seriously, and the uniformity of the powder is lowered. In addition, the excessively high heat treatment temperature has higher requirements on equipment and higher cost, and is not beneficial to subsequent large-scale industrial production. The heat treatment time is too short, so that a good full heat treatment effect cannot be realized; and if the heat treatment time is too long, energy is wasted, the cost is increased, and the subsequent large-scale industrial production is not facilitated. Therefore, the heat treatment temperature and the heat treatment time within the above-described ranges of the present invention can ensure the optimum heat treatment effect.
Further, in the embodiment of the present invention, the mass ratio of the tungsten powder containing Y, the tungsten carbide, the carbon black, and the cobalt powder in step 3 is (50-55): (32-38): (3.3-3.7): (8-12). The tungsten carbide, the carbon black and the cobalt powder are not limited by other materials, and commercially available or self-made tungsten carbide, carbon black and cobalt powder which are well known to those skilled in the art can be adopted. In addition, the inventor researches and discovers that the mass ratio of Y-containing tungsten powder, tungsten carbide, carbon black and cobalt powder is (50-55): (32-38): (3.3-3.7): (8-12), the plate-shaped crystal WC reinforced net-shaped structure hard alloy is easier to prepare.
Further, in the embodiment of the present invention, 2% of paraffin as a forming agent is further added in step 3, and the solid-to-liquid ratio is 2: 1, taking alcohol as a ball milling medium; however, the paraffin, alcohol and the like are not particularly limited in the present invention, and commercially available or self-made paraffin and alcohol known to those skilled in the art may be used.
Further, in the embodiment of the invention, the rotation speed of the ball milling process in the step 3 is 260-300 r/min, the ball milling time is 24-48 h, and the ball-to-material ratio is (4.5-5.5): 1. in addition, the inventor researches and discovers that the plate-shaped crystal WC reinforced network structure hard alloy provided by the invention can be prepared more easily within the range of reasonable ball milling process conditions.
Further, in the embodiment of the present invention, the grinding balls for ball grinding and mixing in step 3 are composed of YG8 cemented carbide balls with two diameters of 3-5mm and 7-9mm, and the mass ratio of the two balls is 1: (3-4). In addition, the inventor researches and discovers that the plate-shaped crystal WC reinforced network structure hard alloy can be prepared more easily by simultaneously using YG8 hard alloy balls with the diameters of 3-5mm and 7-9mm as grinding balls. The reason is that when the single-specification grinding ball is adopted for grinding, the impact point between the ball is small, the gap is large, and the grinding efficiency is low. And adopt two kinds of grinding balls of different diameters size simultaneously then can play fine synergism, can be abundant strike the material, promote the formation of plate-like brilliant.
Further, in the embodiment of the invention, the vacuum drying temperature in the step 3 is 80-110 ℃, and the drying time is 0.5-3 h. Vacuum drying, also known as resolution drying, is a drying method in which a material is placed under negative pressure and is properly heated to reach a boiling point under a negative pressure state or is solidified by cooling so as to dry the material through a melting point. In various heating and drying methods under normal pressure, color, fragrance, taste and nutrient components of the materials are lost to a certain extent due to heating of the materials. If the vacuum drying method is adopted, the air is isolated under the negative pressure state, so that part of materials which are easy to be oxidized and other chemical changes in the drying process can better keep the original characteristics, and the quality loss can be reduced. The vacuum drying equipment is not limited to other specific equipment, and the vacuum drying equipment can be commercially available or homemade vacuum drying equipment well known to those skilled in the art.
Further, in the embodiment of the invention, the pressing pressure in the step 4 is 280-420 MPa, and the pressure maintaining time is 15-20 s.
Further, in the embodiment of the present invention, the sintering in step 4 is performed in a degreasing sintering high-pressure furnace, and the degreasing sintering high-pressure furnace adopted by the present invention can at least withstand a high temperature of 1700 ℃ or higher; the degreasing sintering furnace is not limited to any more, and commercially available or self-made degreasing sintering furnaces well known to those skilled in the art can be used.
Further, in the embodiment of the invention, the temperature of the sintering is increased to 1430-1480 ℃ at the temperature increasing rate of 6-12 ℃, the temperature is maintained for 0.5-2.0 h, and the sintering pressure is 1.0-8.0 MPa. The inventor researches and finds that the plate-shaped crystal WC reinforced network structure hard alloy provided by the invention is easier to prepare within the reasonable sintering temperature and heat preservation time range. If the sintering treatment temperature is too low, the formation and growth of plate-shaped crystal WC grains are not facilitated; and if the sintering treatment temperature is too high, the requirements on equipment are higher, the cost is higher, and the subsequent large-scale industrial production is not facilitated. The heat preservation treatment time is too short, so that a good heat preservation treatment effect cannot be realized; and the heat preservation treatment time is too long, so that energy is wasted, the cost is increased, and the subsequent large-scale industrial production is not facilitated. Therefore, the best sintering treatment effect can be ensured by adopting the sintering treatment temperature and the heat preservation treatment time within the range.
In one aspect of the invention, in an embodiment of the invention, the invention also provides a plate-shaped crystal WC reinforced net-structure hard alloy which is prepared by the method. The invention provides a plate-shaped crystal reinforced net-shaped structure hard alloy, which is characterized in that plate-shaped crystal WC is introduced into the net-shaped structure hard alloy, and the high-temperature fatigue resistance and the corrosion resistance of the plate-shaped crystal are fully utilized, so that the net-shaped hard alloy has stable high-temperature performance and corrosion resistance besides the double-high performance, and the service life of the alloy is greatly prolonged.
In one aspect of the present invention, in the embodiments of the present invention, the cemented carbide prepared by the method of the present invention is widely used in various fields of engineering machinery, machining, aerospace, etc. due to its high hardness, toughness and greatly improved service life.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way. In addition, the percentages recited in the examples are by mass unless otherwise specified.
Example 1:
step 1: the mass ratio of W in ammonium metatungstate to Y in yttrium acetate is tightly matched according to the ratio of 3200: 1, the ammonium metatungstate and yttrium acetate are stirred in pure water to obtain a homogeneous solution, and the solution is spray-dried to obtain precursor powder;
and 2, step: carrying out heat treatment on the precursor in a tubular sintering furnace, sintering the precursor under the action of hydrogen to obtain W powder with uniformly distributed Y elements, wherein the heat treatment process comprises the following steps: heating to 300 deg.C, maintaining for 2h, continuing heating to 1000 deg.C, and maintaining for 6.0 h;
and 3, step 3: and (3) mixing the tungsten powder containing Y, the tungsten carbide, the carbon black and the cobalt powder obtained in the step (2) according to the mass ratio of (50): (38): (3.3): (8) weighing, adding 2% of paraffin as a forming agent, and adding a mixture of 2: 1, taking alcohol as a ball milling medium, and then carrying out ball milling and mixing on the powder. The ball milling process comprises the following steps: rotating speed: 260r/min, the ball milling time is 24h, and the ball-material ratio is (4.5): 1, wherein the grinding ball comprises YG8 hard alloy balls with two diameters, the diameters are 4.5mm and 8mm, the mass ratio of the two balls is 1: (3). And (4) after the ball milling is finished, carrying out vacuum drying at the drying temperature of 80 ℃ for 3h to finally obtain a mixture.
And 4, step 4: and pressing and sintering the mixture to finally obtain the plate-shaped crystal reinforced reticular hard alloy A.
Wherein the pressing pressure is 280MPa, and the pressure is maintained for 15 s; sintering is carried out in a degreasing sintering high-pressure furnace, the temperature is raised to 1430 ℃ at the temperature rise rate of 6 ℃, the temperature is kept for 2.0h, and the sintering pressure is 1.0 MPa.
The images of the samples prepared in example 1 are shown in fig. 1-2, wherein fig. 1 is a microscopic photomicrograph showing that the network is more uniformly distributed in the finer platelets. Fig. 2 is an electron micrograph, from which it can be seen that the plate fraction of WC grains in the entire alloy is high, and both coarse WC and fine WC grains exhibit a relatively complete plate structure. The hard alloy with the plate-shaped crystal reinforced reticular structure prepared by the method has uniform structure, complete WC crystal grain development and excellent performance.
Example 2
Step 1: the mass ratio of W in ammonium metatungstate to Y in yttrium acetate is closely matched according to the ratio of (3500: 1), the ammonium metatungstate and the yttrium acetate are stirred in pure water to obtain a homogeneous solution, and the solution is spray-dried to obtain precursor powder;
step 2: carrying out heat treatment on the precursor in a tubular sintering furnace, and sintering the precursor under the action of hydrogen to obtain W powder with uniformly distributed Y elements, wherein the heat treatment process comprises the following steps: heating to 350 deg.C, maintaining the temperature for 0.5, continuing heating to 1100 deg.C, and maintaining the temperature for 3.0 h;
And 3, step 3: and (3) mixing the tungsten powder containing Y, the tungsten carbide, the carbon black and the cobalt powder obtained in the step (2) according to the mass ratio of (55): (38): (3.7): (12) weighing, adding 2% of paraffin as a forming agent, and adding a solid-liquid ratio of 2: 1, taking alcohol as a ball milling medium, and then carrying out ball milling and mixing on the powder. The ball milling process comprises the following steps: rotating speed: 300r/min, the ball milling time is 48h, and the ball-material ratio is (5.5): 1, wherein the grinding ball comprises YG8 hard alloy balls with two diameters, the diameters are 4.5mm and 8mm, the mass ratio of the two balls is 1: (4). And (4) after the ball milling is finished, carrying out vacuum drying at the drying temperature of 110 ℃ for 3h to finally obtain a mixture.
And 4, step 4: and pressing and sintering the mixture to finally obtain the plate-shaped crystal reinforced reticular hard alloy B.
Wherein the pressing pressure is 420MPa, and the pressure is maintained for 20S; sintering is carried out in a degreasing sintering high-pressure furnace, the temperature is raised to 1480 ℃ at the temperature raising rate of 12 ℃, the temperature is preserved for 0.5h, and the sintering pressure is 8.0 MPa.
Example 3
Step 1: the mass ratio of W in ammonium metatungstate to Y in yttrium acetate is closely matched according to the ratio of (3350: 1), ammonium metatungstate and yttrium acetate are stirred in pure water to obtain a homogeneous solution, and the solution is spray-dried to obtain precursor powder;
Step 2: carrying out heat treatment on the precursor in a tubular sintering furnace, and sintering the precursor under the action of hydrogen to obtain W powder with uniformly distributed Y elements, wherein the heat treatment process comprises the following steps: heating to 330 deg.C, maintaining the temperature for 1.2h, continuing heating to 1050 deg.C, and maintaining the temperature for 4.5 h;
and step 3: and (3) mixing the tungsten powder containing Y, the tungsten carbide, the carbon black and the cobalt powder obtained in the step (2) according to the mass ratio of (53): (35): (3.5): (10) weighing, adding 2% of paraffin as a forming agent, and adding a mixture of 2: 1, taking alcohol as a ball milling medium, and then carrying out ball milling and mixing on the powder. The ball milling process comprises the following steps: rotating speed: 280r/min, the ball milling time is 36h, the ball-material ratio is 5: 1, wherein the grinding ball comprises YG8 hard alloy balls with two diameters, the diameters are 4.5mm and 8mm, the mass ratio of the two balls is 1: 3.5. and (4) after the ball milling is finished, carrying out vacuum drying at the drying temperature of 100 ℃ for 2h to finally obtain a mixture.
And 4, step 4: and pressing and sintering the mixture to finally obtain the plate-shaped crystal reinforced reticular hard alloy C.
Wherein the pressing pressure is 350MPa, and the pressure is maintained for 18S; sintering is carried out in a degreasing sintering high-pressure furnace, the temperature is raised to 1460 ℃ at the temperature raising rate of 10 ℃, the temperature is kept for 1.5h, and the sintering pressure is 5.0 MPa.
Comparative example 1:
the samples were prepared according to the process parameters of example 1, wherein step 1 and step 2 in example 1 were removed, and in step three, the mass ratio of W powder, tungsten carbide, carbon black, cobalt powder and yttrium oxide was directly adjusted according to 49.98: 38: 3.3: 8: 0.02 the procedure was the same as in step 1 except that it was weighed. Finally, sample D was obtained.
From the results of comparative example 1, it can be seen that if the Y element is directly mixed with other raw materials in step 3 without steps 1 and 2, the Y element cannot be uniformly dispersed, and Y element aggregation is easily formed, which results in shortening the service life of the cemented carbide.
Comparative example 2
The procedure was the same as in step 1 except that the ball milling balls in step 3 were changed to YG8 cemented carbide balls having a diameter of 8 mm. Finally, sample E was obtained.
From the results of comparative example 2, it can be seen that if the single-size grinding balls are used, the grinding efficiency is reduced, which is not favorable for flattening the WC powder, thereby reducing the plate fraction, resulting in a reduction in the service life of the cemented carbide.
Comparative example 3:
samples were prepared according to the process parameters of example 1, except that no yttrium acetate was added in step 1, to give final sample F.
From the results of comparison 3, it can be seen that if yttrium element is not doped, the formation of WC plate-like crystals is not facilitated, thereby resulting in the shortened service life of the cemented carbide.
Comparative example 4:
a sample was prepared according to the process parameters of example 1 except that yttrium acetate was changed to lanthanum acetate in step 1, and finally sample G was obtained.
From the results of comparison 4, it can be seen that the lanthanum element has no effect of the yttrium element in promoting the formation of plate-shaped crystals, thereby causing the reduction of the plate-shaped rate of WC grains in the hard alloy, and causing the service life of the hard alloy to be shortened.
The samples prepared in the examples and the comparative examples were tested, 5 samples were respectively mounted on a three-SR 360R rotary drilling rig and a 1.2m drill barrel for rotary drilling operation, and the test results were as follows:
TABLE 1 test results
As can be seen from the test results in Table 1, the plate-shaped crystal reinforced network-structure hard alloy samples prepared by the method of the invention have no crack, and the maximum wear and the minimum wear are relatively small, so the service life is relatively longer.
The foregoing examples are merely illustrative of and explain the present invention and are not to be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Claims (10)
1. A preparation method of plate-shaped crystal reinforced reticular structure hard alloy is characterized by comprising the following steps:
Step 1: stirring and mixing soluble tungsten salt and soluble yttrium salt in a solvent to obtain a homogeneous solution, and performing spray drying on the solution to obtain precursor powder;
and 2, step: carrying out heat treatment on the precursor powder to obtain tungsten powder containing Y;
and 3, step 3: ball-milling and mixing Y-containing tungsten powder, tungsten carbide, carbon black and cobalt powder, and then carrying out vacuum drying to obtain a mixture;
and 4, step 4: and pressing and sintering the mixture to obtain the plate-shaped crystal reinforced reticular hard alloy.
2. The method according to claim 1, wherein the soluble tungsten salt in step 1 is ammonium metatungstate; in the step 1, the soluble yttrium salt is yttrium acetate; the solvent in the step 1 is pure water; the mass ratio of W in the soluble tungsten salt to Y in the soluble yttrium salt in the step 1 is (3200-.
3. The production method according to claim 1, wherein the heat treatment in step 2 is performed in a tube sintering furnace; and in the step 2, sintering is carried out under the action of hydrogen to obtain W powder with uniformly distributed Y elements.
4. The method according to claim 1, wherein the heat treatment process in step 2 is: heating to 300-350 ℃, keeping the temperature for 0.5-2 h, continuously heating to 1000-1100 ℃, and keeping the temperature for 3.0-6.0 h.
5. The preparation method according to any one of claims 1 to 4, wherein the mass ratio of the Y-containing tungsten powder to the tungsten carbide to the carbon black to the cobalt powder in step 3 is (50-55): (32-38): (3.3-3.7): (8-12).
6. The preparation method according to any one of claims 1 to 4, wherein paraffin is further added as a forming agent in the step 3, and alcohol is added as a ball milling medium; in the step 3, the rotation speed of the ball milling process is 260-300 r/min, the ball milling time is 24-48 h, and the ball material ratio is (4.5-5.5): 1.
7. the production method according to any one of claims 1 to 4, wherein the milling balls of the ball mill blend in the step 3 are composed of YG8 cemented carbide balls of two diameters of 3 to 5mm and 7 to 9mm, and the mass ratio of the two balls is 1: (3-4).
8. The method according to any one of claims 1 to 4, wherein the vacuum drying temperature in step 3 is 80 to 110 ℃ and the drying time is 0.5 to 3 hours; in the step 4, the pressing pressure is 280-420 MPa, and the pressure maintaining time is 15-20 s.
9. The preparation method according to any one of claims 1 to 4, wherein the sintering in step 4 is carried out in a degreasing sintering high-pressure furnace, the sintering is carried out at a temperature rise rate of 6 to 12 ℃ to 1430 to 1480 ℃ and at a temperature preservation time of 0.5 to 2.0h, and the sintering pressure is 1.0MPa to 8.0 MPa.
10. A plate-shaped grain-reinforced network-structured cemented carbide produced by the method according to any one of claims 1 to 9.
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