CN114293053B - Tungsten steel ceramic hard alloy and preparation method thereof - Google Patents
Tungsten steel ceramic hard alloy and preparation method thereof Download PDFInfo
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Abstract
The invention provides a tungsten steel ceramic hard alloy and a preparation method thereof, belonging to the technical field of hard alloys. The method comprises the following steps: s1, uniformly mixing WC powder, Ni powder, Fe-Si-Al oxide nano powder and an inhibitor in 97# gasoline to obtain a mixture; s2, adding 97# gasoline into the mixture, carrying out ball milling, and sieving to obtain mixed slurry; s3, adding carboxymethyl cellulose serving as a forming agent into the mixed slurry, carrying out ball milling, and drying to obtain powder; 4. putting the powder into a die, extruding and drying to obtain a blank; and S5, performing discharge plasma sintering on the blank, discharging, cooling and sand blasting to obtain the tungsten steel ceramic hard alloy. The tungsten steel ceramic hard alloy prepared by the invention has good corrosion resistance, heat resistance, high-temperature oxidation resistance, excellent abrasion resistance, good toughness, strength and bending resistance, high hardness, high density, fine and uniform tissue and wide application prospect.
Description
Technical Field
The invention relates to the technical field of hard alloy, in particular to tungsten steel ceramic hard alloy and a preparation method thereof.
Background
The hard alloy is an alloy material which is formed by sintering tungsten carbide, titanium carbide or a compound carbide formed by the tungsten carbide and the titanium carbide as a hard phase and cobalt as a binding phase through a powder metallurgy process and a high-temperature liquid phase. 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 the temperature of 500 ℃, and still has high hardness at the temperature of 1000 ℃.
The tungsten resources in China account for more than 65% of the world tungsten resources, wherein the Jiangxi is famous for the tungsten community. The industrial development of tungsten in China mainly starts in the thirties of the twentieth century, and the development of tungsten processing technology obtains huge achievements. Since the industry of China started late, China is an advanced line in the world in the aspects of initial processing and smelting of tungsten, but has a certain gap with foreign countries in the technology of hard alloy products. In the production technology of hard alloy, tungsten carbide and cobalt powder are mainly used as raw materials, and the raw materials are formed in a glue-doped or wax-doped mode. Sintering at 1200 deg.C or higher. Because of the granularity factors of the tungsten carbide and the cobalt powder and the different proportion of the tungsten carbide and the cobalt powder, the properties of the sintered hard alloy are far from each other. Therefore, the cemented carbide grades are also different.
When the hard alloy is manufactured, the granularity of the selected raw material powder is between 1 and 2 microns, and the purity is very high. The raw materials are proportioned, added with alcohol or other medium, wet-milled in a wet ball mill, fully mixed and pulverized, dried, sieved, added with forming agent such as wax or glue, dried and sieved to obtain the mixture. When the mixture is pelletized, pressed and heated to a temperature close to the melting point of the binder metal (1300 ℃ and 1500 ℃), the hardened phase and the binder metal form eutectic alloy. Upon cooling, the hardening phases are distributed in the network of binder metal and are intimately associated with each other to form a solid whole. The hardness of cemented carbides depends on the hard phase content and grain size, i.e. the higher the hard phase content, the finer the grains, the greater the hardness. The toughness of the hard alloy with reduced junction temperature is determined by the bonding metal, and the higher the content of the bonding metal is, the higher the bending strength is.
The traditional preparation method of the hard alloy comprises the steps of carrying out solid-phase reaction on tungsten powder and carbon powder at 1400-1600 ℃ to generate tungsten carbide, then mixing the tungsten carbide with cobalt powder, carrying out ball milling, carrying out cold press molding, and finally carrying out liquid-phase sintering densification. The alloy crystal grain obtained by the preparation method is generally 1um-10um, and has the problems of large brittleness, processing softening and the like. While adjusting the tungsten carbide/cobalt composition may improve certain properties of the final part, for example, increasing the tungsten carbide content increases the hardness of the part to increase wear and corrosion resistance; increasing the cobalt content increases the strength toughness and improves the processability. However, it has long been difficult to improve the strength and toughness while increasing the hardness.
The conversion of cemented carbide from traditional to ultra-fine and nano-scale has become its trend, and the research of ultra-fine cemented carbide and nano-scale cemented carbide has been a hot problem in the field of high performance cemented carbide in the past decade. However, the excessive pursuit of preparing nano or superfine hard alloy leads to the rapid increase of the cost, the obtained effect is not very obvious, and the grain growth in the sintering process is difficult to control when the powder metallurgy is used for producing the hard alloy by the traditional process, so that the hard alloy with fine grains is very difficult to obtain.
At present, the production process of the large complex anisotropic product of the hard alloy mainly comprises two types:
one is to press the mixture, including mould pressing and cold isostatic pressing, and then sinter to produce hard alloy blank, the machining allowance after sintering is very large, and the machining difficulty is large, the time consumption is long, and the method is not economical; the other is a hot pressing process which is completed by loading the mixture in a graphite die, pressing and sintering at one time. The hot pressing process has the features of high product density, high performance, low pressing pressure and capacity of producing large product. But the shape of the product is limited, only products with simple shapes can be prepared, and the process is only suitable for single-piece or small-batch production, and has low production rate and high cost. Injection molding is widely used as a near-net-shape forming process in the preparation of small-sized hard alloy parts with complicated shapes, but the injection molding technology has many defects, such as tedious degumming process, high degumming rejection rate, low product strength and the like, and high requirements on equipment and molds, and the fact proves that the injection molding can only prepare small-sized parts.
US5918102A discloses an ultra-fine grain hard alloy for a tape cutter, which takes Co, Ni or their alloy with the content of 6-15 wt% as a binding phase, and TiC, TaC, NbC, HfC, ZrC, Mo and less than or equal to 1.0 wt% are added2One or more of C, VC and the like are used as grain growth inhibitors, and the superfine hard alloy with the grain size less than or equal to 0.6 mu m (-0.4 mu m) is obtained by sintering under the low-pressure hot isostatic pressing at the temperature of about 1400 ℃.
US6511551B2 discloses a method for adding a grain growth inhibitor during the preparation of an ultra-fine grain WC-Co hard alloy, wherein a method of adding water-soluble salts of V, Ta and Cr elements into W, Co water-soluble salts is adopted to introduce the components of the grain growth inhibitor, and the method can greatly improve the dispersion uniformity of the grain growth inhibitor, thereby more effectively inhibiting the uneven growth of grains and further greatly improving the mechanical properties of the alloy.
US9005329B2 discloses a fine grain WC-Co hard alloy and a preparation method thereof, the content of Co + Cr is 3-15 wt%, the weight ratio of Cr/Co is 0.05-0.15, and simultaneously, Ti, V, Zr, Ta or Nb and the like with extremely small quantity (ppm level) are singly or compositely added as grain growth inhibitors.
EP1803830B1 discloses a cemented carbide with a grain size of 0.3 μm or less and a binder phase content of 5.5 to 15 wt.%, with addition of Ti in an amount of 0.005 to 0.06 wt.% (preferably 0.01 to 0.04 wt.%), and Cr (the ratio of the amount of Cr to the binder phase content is 0.04 to 0.2) as grain growth inhibitor, without addition of Ta.
CN101629263B discloses an ultra-fine grain hard alloy, which comprises 8.0-9.0 wt% of Co, 0.5-1.0 wt% of TaC and the balance of 0.3-2.0 wt% of Cr3C2The WC of (1). 3-6 parts of ball material: 1, using alcohol as a wet grinding medium, wet grinding for 60-80 hours under the condition that the liquid-solid ratio is 500ml/kg and the liquid-solid ratio is 300-.
Disclosure of Invention
The invention aims to provide a tungsten steel ceramic hard alloy and a preparation method thereof, which have the advantages of good corrosion resistance, heat resistance, high-temperature oxidation resistance, excellent wear resistance, good toughness, strength and bending resistance, high hardness, high density, fine and uniform tissue and wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of tungsten steel ceramic hard alloy, which comprises the following steps:
s1, uniformly mixing WC powder, Ni powder, Fe-Si-Al oxide nano powder and an inhibitor in a 97# gasoline medium to obtain a mixture;
s2, adding 97# gasoline as a medium into the mixture obtained in the step S1 for primary ball milling, and sieving the mixture through a 400-sand 500-mesh sieve to obtain mixed slurry;
s3, adding carboxymethyl cellulose serving as a forming agent into the mixed slurry obtained in the step S2, performing secondary ball milling, and performing primary drying to obtain powder;
s4, putting the powder in the step S3 into a die for extrusion, and drying for the second time to obtain a blank;
and S5, performing discharge plasma sintering on the blank prepared in the step S4, discharging, cooling and sandblasting to prepare the tungsten steel ceramic hard alloy.
As a further improvement of the invention, the preparation method of the Fe-Si-Al oxide nanopowder comprises the following steps:
(1) porous SiO2/Al2O3Preparing hollow nano microspheres: dissolving aminosilane and aluminum isopropoxide in ethyl acetate to obtain an oil phase; dissolving a pore-foaming agent and a surfactant in water to obtain a water phase; adding the oil phase into the water phase, emulsifying, adjusting the pH value of the solution to 8-9, reacting for 7-12h, centrifuging, washing the solid, drying and calcining to obtain porous SiO2/Al2O3Hollow nano-microspheres;
(2) preparation of Fe-Si-Al oxide nanopowder: dissolving ferric nitrate in water, adding citric acid and the porous SiO prepared in the step (1)2/Al2O3Carrying out ultrasonic dispersion on hollow nano microspheres, and heating to 50-60 ℃ to evaporate a solvent to obtain sol; then raising the temperature to 180 ℃ and 200 ℃ and keeping the vacuum degree at 0.01-0.1MPa to form dry gel, taking out the dry gel, and igniting the dry gel to obtain the Fe-Si-Al oxide nano powder.
As a further improvement of the invention, the content of the pore-foaming agent in the aqueous phase is 1-2 wt%; the content of the surfactant is 2-4 wt%; the pore-foaming agent is selected from at least one of cetyl trimethyl ammonium bromide, oxyethylene-oxypropylene triblock copolymer PEO20-PPO70-PEO20 and PEO106-PPO70-PEO 106; the surfactant is selected from at least one of tween-80, tween-20, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium hexadecyl benzene sulfonate, sodium hexadecyl sulfate and sodium octadecyl sulfonate; the emulsification condition is that the emulsification is carried out for 3-5min at the rotating speed of 10000-; the calcination temperature is 400-500 ℃ and the time is 2-4 h.
As a further improvement of the invention, the mass ratio of the aminosilane to the aluminum isopropoxide is (2-5): 10; the mass ratio of the citric acid to the ferric nitrate is (2-4): 1; the mass ratio of the ferric nitrate to the porous SiO2/Al2O3 hollow nano microsphere is 2: (3-5).
Further, the aminosilane is selected from at least one of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) -gamma-aminopropyltriethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldiethoxysilane and diethylenetriaminopropyltrimethoxysilane.
As a further improvement of the invention, the inhibitor is selected from TiC, VC, TaC and LaC2、Cr3C2At least one of (1).
As a further improvement of the invention, the inhibitors are TaC, TiC and LaC2The mass ratio of the mixture of (1) to (3): (1-2): (0.2-0.5).
As a further improvement of the invention, the content of the WC powder is 82-90 wt%; the weight percentage content of the Ni powder is 7-12 wt%; the weight percentage content of the Fe-Si-Al oxide nano powder is 3-6 wt%; the weight percentage content of the inhibitor is 0.2-0.5 wt%.
As a further improvement of the invention, the solid-to-liquid ratio of the total mass of the WC powder, the Ni powder, the Fe-Si-Al oxide nanopowder and the inhibitor in the step S1 to the 97# gasoline is 1: (0.8-1.1) g/mL; the solid-liquid ratio of the mixture to 97# gasoline in the step S2 is 1: (0.4-0.6) g/mL; the first ball milling condition is that hard alloy balls with the diameter of 6-10mm are used as grinding bodies, and the ball-to-material ratio is (10-12): 1, ball milling rotation speed is 72-77% of critical rotation speed, and ball milling time is 36-48 h; in the step S3, the addition amount of the carboxymethyl cellulose is 2-3wt% of the mixed slurry; the conditions of the second ball milling are that hard alloy balls with the diameter of 6-10mm are used as grinding bodies, and the ball-to-material ratio is (7-10): 1, ball milling rotation speed is 70-74% of critical rotation speed, and ball milling time is 12-24 h; the first drying temperature is 70-85 ℃, and the time is 3-5 h; in the step S4, the extrusion pressure is 120-270MPa, the secondary drying temperature is 30-50 ℃, and the time is 4-5 h; the sintering condition of the discharge plasma in the step S5 is 1100-1300 ℃, and the discharge is performed for 5-10min under the pressure of 30-50 MPa.
As a further improvement of the invention, the method specifically comprises the following steps:
s1, mixing 82-90wt% of WC powder, 7-12wt% of Ni powder, 3-6wt% of Fe-Si-Al oxide nano powder and 0.2-0.5wt% of inhibitor in a 97# gasoline medium in a mixer at 8000-10000r/min for 10-20min, wherein the total mass of the WC powder, the Ni powder, the Fe-Si-Al oxide nano powder and the inhibitor is 1: (0.8-1.1) g/mL to give a mixture;
wherein the inhibitor is TaC, TiC and LaC2The mass ratio of the mixture of (1) to (3): (1-2): (0.2-0.5);
s2, adding 97# gasoline into the mixture obtained in the step S1, wherein the solid-to-liquid ratio of the mixture to the 97# gasoline is 1: (0.4-0.6) g/mL, and performing ball milling under the conditions that hard alloy balls with the diameter of 6-10mm are adopted as grinding bodies, and the ball-to-material ratio is (10-12): 1, ball milling at a rotating speed of 72-77% of the critical rotating speed for 36-48h, and sieving the mixture through a 400-sand 500-mesh sieve to obtain mixed slurry;
s3, adding carboxymethyl cellulose into the mixed slurry obtained in the step S2 to serve as a forming agent, wherein the addition amount of the carboxymethyl cellulose is 2-3wt% of the mixed slurry, and performing ball milling under the condition that hard alloy balls with the diameter of 6-10mm are adopted as grinding bodies, and the ball-to-material ratio is (7-10): 1, ball milling at 70-74% of critical speed for 12-24h, and drying at 70-85 ℃ for 3-5h to obtain powder;
s4, putting the powder in the step S3 into a die, extruding under the pressure of 120 and 270MPa, and drying at 30-50 ℃ for 4-5h to obtain a blank;
s5, performing discharge plasma sintering on the blank prepared in the step S4 under the conditions of 1100-1300 ℃ and 30-50MPa for 5-10min of discharge, discharging, cooling and sand blasting to prepare the tungsten steel ceramic hard alloy.
The invention further protects the tungsten steel ceramic hard alloy prepared by the preparation method.
The invention has the following beneficial effects: the invention prepares Fe-Si-Al oxide nano powder by a sol-gel method, and firstly prepares porous SiO2/Al2O3In the preparation process of the hollow nano-microsphere, oil-in-water generates sol-gel reaction at an oil-water interface, the interior is continuously consumed to form a shell layer, under the action of a pore-forming agent and a surfactant, porous hollow microspheres are formed, a nitrate-citric acid reaction system is added, a solution enters the pores of the microspheres to fill the microspheres, and on the other hand, citric acid is weak acid and generates multi-stage dissociation reaction, and Fe ions are generated in the metal ions3+In the presence of a complex, the reaction is as follows:
Fe3++C6H5O7 3-=FeC6H5O7
Fe3++C6H6O7 2-=FeC6H6O7 +
because citric acid is weak acid, chemical equilibrium displacement exists in the reaction process, and the citric acid is excessive at the moment, so that stable complexation of metal ions and the citric acid is ensured. The xerogel is burnt to obtain Fe-Si-Al oxide nanopowder, the obtained Fe-Si-Al oxide nanopowder is used as a binder enhancer together with binder Ni to replace Co as a binder phase, so that the harm to the environment and human health caused by the addition of Co can be avoided, and the binder is subjected to solid solution strengthening or second phase precipitation strengthening, so that the alloy is strengthened, wherein the Al element and the binder phase Ni form gamma' -phase Ni in the sintering process3Al, and a gamma' phase (100 nm) can be fully precipitated in a bonding phase through solution treatment and aging treatment, so that the alloy strengthening effect is realized, and the performance of the alloy is improved; the addition of Si forms second phase reinforcement, so that the bending strength and Vickers hardness of the alloy are improved; meanwhile, the prepared hard alloy has better corrosion resistance, heat resistance, high-temperature oxidation resistance, excellent abrasion resistance and better alloy toughness. The Fe-Si-Al oxide nano powder prepared by the sol-gel method is used for uniformly mixing all elements to obtain nano powder, the nano powder without hard agglomeration is easily and uniformly mixed around the tungsten carbide powder in the ball milling process, and the abnormal growth of WC can be avoided during reduction.
The invention is realized by addingTaC, TiC and LaC in appropriate proportions2By LaC2TiC and TaC can be dissolved in binding phase to reduce the solubility of WC in binding phase and prevent the crystal grain growth caused by WC dissolution, and TaC and LaC2Segregation occurs at a WC/bonding phase interface, the interface energy is reduced, dissolved WC is prevented from being separated out on the surface of a crystal grain, the rapid growth behavior of the WC crystal grain is inhibited, the introduction of structural defects such as pores and brittleness in the alloy is avoided, and the growth of the crystal grain is inhibited, so that the strength, toughness and other properties of the hard alloy are improved, and the addition of Ti can cause partial slabbiness of the WC crystal grain, because titanium is partialized on the interface to change the interface energy, so that the shape of the WC crystal grain is greatly changed, and the partially slabby WC hard alloy has higher hardness, better breakage resistance and thermal crack resistance, good plastic deformation resistance, less creep deformation and more excellent thermal deformation resistance; the addition of the three components has the function of synergy.
The method for preparing the nano hard alloy by using the spark plasma sintering method can realize rapid temperature rise and fall, short-time sintering, high densification degree of the alloy, and effective inhibition of growth of crystal grains, and finally obtains the hard alloy with fine and uniform tissue, high densification and excellent performance.
The tungsten steel ceramic hard alloy prepared by the invention has the advantages of good corrosion resistance, heat resistance, high-temperature oxidation resistance, excellent abrasion resistance, good toughness, strength and bending resistance, high hardness, high density, fine and uniform tissue and wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a view showing a porous SiO film obtained in preparation example 12/Al2O3Hollow nanometer micro-meterSEM images of spheres;
FIG. 2 is an SEM photograph of the Fe-Si-Al oxide nanopowder obtained in preparation example 1;
FIG. 3 is an SEM photograph of a tungsten steel ceramic cemented carbide block produced in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Preparation example 1
The preparation method of the Fe-Si-Al oxide nano powder comprises the following steps:
(1) porous SiO2/Al2O3Preparing hollow nano microspheres: 2g of gamma-aminopropyltrimethoxysilane and 10g of aluminum isopropoxide are dissolved in 50mL of ethyl acetate to form an oil phase; the content of the prepared ethylene oxide-propylene oxide triblock copolymer PEO106-PPO70-PEO106 is 1 wt%; the aqueous solution with the content of sodium dodecyl benzene sulfonate of 2 weight percent is a water phase; adding 50mL of oil phase into 100mL of water phase, emulsifying for 3min at the rotation speed of 10000r/min, adjusting the pH value of the solution to 8, reacting for 7h, centrifuging for 15min at 3000r/min, washing the solid with deionized water, drying for 5h at 70 ℃, and calcining for 2h at 400 ℃ to obtain porous SiO2/Al2O3Hollow nano-microspheres; FIG. 1 shows the porous SiO obtained2/Al2O3The SEM image of the hollow nano microsphere shows that the particle size of the prepared microsphere is within 100nm, and a large number of pore channels are formed on the surface of the shell layer.
(2) Preparation of Fe-Si-Al oxide nanopowder: dissolving 2g of ferric nitrate in 100mL of water, and adding 4g of citric acid and 3g of porous SiO prepared in step (1)2/Al2O3Carrying out ultrasonic dispersion on hollow nano microspheres for 20min at 1000W, heating to 50 ℃, and evaporating the solvent for 2h to obtain sol; then raising the temperature to 180 ℃ and keeping the vacuum degree at 0.01MPa to form dry gel, taking out the dry gel, and igniting the dry gel to obtainFe-Si-Al oxide nanopowder. FIG. 2 is an SEM image of the obtained Fe-Si-Al oxide nanopowder, which shows that the particle size of the obtained Fe-Si-Al oxide nanopowder is within 150 nm.
Preparation example 2
The preparation method of the Fe-Si-Al oxide nano powder comprises the following steps:
(1) porous SiO2/Al2O3Preparing hollow nano microspheres: dissolving 5g of N-beta (aminoethyl) -gamma-aminopropylmethyldiethoxysilane and 10g of aluminum isopropoxide in 50mL of ethyl acetate to obtain an oil phase; the content of the prepared ethylene-propylene oxide triblock copolymer PEO20-PPO70-PEO20 is 2 weight percent; the aqueous solution with the content of the hexadecyl sodium benzene sulfonate of 4wt percent is a water phase; adding 50mL of oil phase into 100mL of water phase, emulsifying for 5min at the rotating speed of 15000r/min, adjusting the pH value of the solution to 9, reacting for 12h, centrifuging for 15min at 3000r/min, washing the solid with deionized water, drying for 5h at 70 ℃, and calcining for 4h at 500 ℃ to obtain porous SiO2/Al2O3Hollow nano-microspheres;
(2) preparation of Fe-Si-Al oxide nanopowder: dissolving 2g of ferric nitrate in 100mL of water, adding 8g of citric acid and 5g of porous SiO prepared in step (1)2/Al2O3Carrying out ultrasonic dispersion on hollow nano microspheres for 20min at 1000W, heating to 60 ℃, and evaporating the solvent for 2h to obtain sol; then raising the temperature to 200 ℃ and keeping the vacuum degree at 0.1MPa to form dry gel, taking out the dry gel, and igniting the dry gel to obtain the Fe-Si-Al oxide nano powder.
Preparation example 3
The preparation method of the Fe-Si-Al oxide nano powder comprises the following steps:
(1) porous SiO2/Al2O3Preparing hollow nano microspheres: dissolving 3.5g of N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 10g of aluminum isopropoxide in 50mL of ethyl acetate to obtain an oil phase; preparing 1.5wt% of hexadecyl trimethyl ammonium bromide; an aqueous solution containing 3wt% of sodium octadecyl sulfonate is used as a water phase; adding 50mL of oil phase into 100mL of water phase, emulsifying for 4min at the rotating speed of 12500r/min, adjusting the pH value of the solution to 8.5, and reactingCentrifuging for 15min at 3000r/min for 10h, washing the solid with deionized water, drying at 70 ℃ for 5h, and calcining at 450 ℃ for 3h to obtain porous SiO2/Al2O3Hollow nano-microspheres;
(2) preparation of Fe-Si-Al oxide nanopowder: dissolving 2g of ferric nitrate in 100mL of water, and adding 6g of citric acid and 4g of porous SiO prepared in step (1)2/Al2O3Carrying out ultrasonic dispersion on hollow nano microspheres for 20min at 1000W, heating to 55 ℃, and evaporating the solvent for 2h to obtain sol; then raising the temperature to 190 ℃ and keeping the vacuum degree at 0.05MPa to form dry gel, taking out the dry gel, and igniting the dry gel to obtain the Fe-Si-Al oxide nano powder.
Comparative preparation example 1
Compared with preparation example 3, N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane was not added, and other conditions were not changed.
The preparation method of the Fe-Al oxide nano powder comprises the following steps:
(1) porous Al2O3Preparing hollow nano microspheres: dissolving 13.5g of aluminum isopropoxide in 50mL of ethyl acetate to obtain an oil phase; preparing 1.5wt% of hexadecyl trimethyl ammonium bromide; an aqueous solution containing 3wt% of sodium octadecyl sulfonate is used as a water phase; adding 50mL of oil phase into 100mL of water phase, emulsifying for 4min at the rotating speed of 12500r/min, adjusting the pH value of the solution to 8.5, reacting for 10h, centrifuging for 15min at 3000r/min, washing the solid with deionized water, drying for 5h at 70 ℃, calcining for 3h at 450 ℃ to obtain porous Al2O3Hollow nano-microspheres;
(2) preparation of Fe-Al oxide nanopowder: dissolving 2g of ferric nitrate in 100mL of water, and adding 6g of citric acid and 4g of porous Al prepared in step (1)2O3Carrying out ultrasonic dispersion on hollow nano microspheres for 20min at 1000W, heating to 55 ℃, and evaporating the solvent for 2h to obtain sol; then raising the temperature to 190 ℃ and keeping the vacuum degree at 0.05MPa to form dry gel, taking out the dry gel, and igniting the dry gel to obtain the Fe-Al oxide nano powder.
Comparative preparation example 2
Compared with preparation example 3, no aluminum isopropoxide was added, and other conditions were not changed.
The preparation method of the Fe-Si oxide nano powder comprises the following steps:
(1) porous SiO2Preparing hollow nano microspheres: dissolving 13.5g of N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane in 50mL of ethyl acetate to obtain an oil phase; preparing 1.5wt% of hexadecyl trimethyl ammonium bromide; an aqueous solution containing 3wt% of sodium octadecyl sulfonate is used as a water phase; adding 50mL of oil phase into 100mL of water phase, emulsifying for 4min at the rotating speed of 12500r/min, adjusting the pH value of the solution to 8.5, reacting for 10h, centrifuging for 15min at 3000r/min, washing the solid with deionized water, drying for 5h at 70 ℃, calcining for 3h at 450 ℃ to obtain porous SiO2Hollow nano-microspheres;
(2) preparation of Fe-Si oxide nanopowder: dissolving 2g of ferric nitrate in 100mL of water, and adding 6g of citric acid and 4g of porous SiO prepared in step (1)2Carrying out ultrasonic dispersion on hollow nano microspheres for 20min at 1000W, heating to 55 ℃, and evaporating the solvent for 2h to obtain sol; then raising the temperature to 190 ℃ and keeping the vacuum degree at 0.05MPa to form dry gel, taking out the dry gel, and igniting the dry gel to obtain the Fe-Si oxide nano powder.
Comparative preparation example 3
Step S1 was not performed, and other conditions were not changed, compared with preparation example 3.
Preparation of Fe oxide nanopowder: dissolving 2g of ferric nitrate in 100mL of water, adding 6g of citric acid, ultrasonically dispersing for 20min at 1000W, heating to 55 ℃, and evaporating the solvent for 2h to obtain sol; then raising the temperature to 190 ℃ and keeping the vacuum degree at 0.05MPa to form dry gel, taking out the dry gel, and igniting the dry gel to obtain the Fe oxide nano powder.
Comparative preparation example 4
Step S2 was not performed, and other conditions were not changed, compared with preparation example 3.
Porous SiO2/Al2O3Preparing hollow nano microspheres: 3.5g of N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane and 10g of aluminum isopropoxide were dissolved in 50mL of ethyl acetate as the oil phase; preparing the content of hexadecyl trimethyl ammonium bromide1.5 wt%; an aqueous solution containing 3wt% of sodium octadecyl sulfonate is used as a water phase; adding 50mL of oil phase into 100mL of water phase, emulsifying for 4min at the rotating speed of 12500r/min, adjusting the pH value of the solution to 8.5, reacting for 10h, centrifuging for 15min at 3000r/min, washing the solid with deionized water, drying for 5h at 70 ℃, calcining for 3h at 450 ℃ to obtain porous SiO2/Al2O3Hollow nano-microspheres.
Example 1
The embodiment provides a preparation method of tungsten steel ceramic hard alloy, which comprises the following steps:
s1, taking 89wt% of WC powder, 7wt% of Ni powder, 3.8wt% of Fe-Si-Al oxide nano powder prepared in preparation example 1 and 0.2wt% of inhibitor, and stirring and mixing for 10min in a 97# gasoline medium in a mixer at 8000r/min, wherein the solid-to-liquid ratio of the total mass of the WC powder, the Ni powder, the Fe-Si-Al oxide nano powder and the inhibitor to the 97# gasoline is 1: 0.8g/mL to give a mixture;
wherein the inhibitor is TaC, TiC and LaC2The mass ratio of (3): 1: 0.2;
s2, adding 97# gasoline into the mixture obtained in the step S1, wherein the solid-to-liquid ratio of the mixture to the 97# gasoline is 1: 0.4g/mL, performing ball milling under the condition that a hard alloy ball with the diameter of 10mm is adopted as a grinding body, wherein the ball-to-material ratio is 10: 1, ball milling at a rotating speed of 72 percent of critical rotating speed for 36 hours, and sieving the mixture through a 400-mesh sieve to obtain mixed slurry;
s3, adding carboxymethyl cellulose into the mixed slurry obtained in the step S2 to serve as a forming agent, wherein the addition amount of the carboxymethyl cellulose is 2wt% of the mixed slurry, and performing ball milling under the conditions that hard alloy balls with the diameter of 10mm are adopted as grinding bodies, and the ball-to-material ratio is 7: 1, ball milling at 70% of critical speed for 12h, and drying at 70 ℃ for 3h to obtain powder;
s4, putting the powder in the step S3 into a die, extruding under the pressure of 120MPa, and drying at 30-50 ℃ for 4h to obtain a blank;
s5, performing discharge plasma sintering on the blank prepared in the step S4 under the condition of discharging at 1100 ℃ and 30MPa for 5min, discharging, cooling and blasting sand to prepare the tungsten steel ceramic hard alloy. FIG. 3 is an SEM image of the obtained W-steel ceramic hard alloy, which shows that the compactness of the block is high, the average grain size is within 500nm, the grain size distribution is uniform, and abnormal growth of grains is avoided.
Example 2
The embodiment provides a preparation method of tungsten steel ceramic hard alloy, which comprises the following steps:
s1, taking 82.5wt% of WC powder, 11wt% of Ni powder, 6wt% of Fe-Si-Al oxide nano powder prepared in preparation example 2 and 0.5wt% of inhibitor, and stirring and mixing for 20min in a 97# gasoline medium at 10000r/min in a mixer, wherein the solid-to-liquid ratio of the total mass of the WC powder, the Ni powder, the Fe-Si-Al oxide nano powder and the inhibitor to the 97# gasoline is 1: 1.1g/mL to give a mixture;
wherein the inhibitor is TaC, TiC and LaC2The mass ratio of the mixture of (1) to (3): 2: 0.5;
s2, adding 97# gasoline into the mixture obtained in the step S1, wherein the solid-to-liquid ratio of the mixture to the 97# gasoline is 1: 0.6g/mL, performing ball milling under the conditions that hard alloy balls with the diameter of 6mm are adopted as grinding bodies, and the ball-to-material ratio is 12: 1, ball milling at a rotational speed of 77% of a critical rotational speed for 48 hours, and sieving the mixture through a 500-mesh sieve to obtain mixed slurry;
s3, adding carboxymethyl cellulose into the mixed slurry obtained in the step S2 to serve as a forming agent, wherein the addition amount of the carboxymethyl cellulose is 3wt% of the mixed slurry, and performing ball milling under the conditions that hard alloy balls with the diameter of 6mm are adopted as grinding bodies, and the ball-to-material ratio is 10: 1, ball milling at a rotating speed of 74% of a critical rotating speed for 24 hours, and drying at 85 ℃ for 5 hours to obtain powder;
s4, putting the powder in the step S3 into a die, extruding under the pressure of 270MPa, and drying at 50 ℃ for 5 hours to obtain a blank;
s5, performing discharge plasma sintering on the blank prepared in the step S4 under the condition of 1300 ℃ and 50MPa for 10min, discharging, cooling, and performing sand blasting to obtain the tungsten steel ceramic hard alloy.
Example 3
The embodiment provides a preparation method of tungsten steel ceramic hard alloy, which comprises the following steps:
s1, 84.65wt% of WC powder, 10wt% of Ni powder, 5wt% of Fe-Si-Al oxide nano powder prepared in preparation example 3 and 0.35wt% of inhibitor are taken to be stirred and mixed for 15min in a 97# gasoline medium in a mixer at 9000r/min, and the solid-to-liquid ratio of the total mass of the WC powder, the Ni powder, the Fe-Si-Al oxide nano powder and the inhibitor to the 97# gasoline is 1: 1g/mL to obtain a mixture;
wherein the inhibitor is TaC, TiC and LaC2The mass ratio of the mixture of (1) to (3): 1.5: 0.35;
s2, adding 97# gasoline into the mixture obtained in the step S1, wherein the solid-to-liquid ratio of the mixture to the 97# gasoline is 1: 0.5g/mL, performing ball milling under the condition that hard alloy balls with the diameter of 8mm are used as grinding bodies, wherein the ball-to-material ratio is 11: 1, ball milling at 75% of critical speed for 40h, and sieving the mixture through a 500-mesh sieve to obtain mixed slurry;
s3, adding carboxymethyl cellulose into the mixed slurry obtained in the step S2 to serve as a forming agent, wherein the addition amount of the carboxymethyl cellulose is 2.5wt% of the mixed slurry, and performing ball milling under the condition that hard alloy balls with the diameter of 6-10mm are adopted as grinding bodies, wherein the ball-to-material ratio is 8: 1, ball milling at a rotating speed of 72 percent of a critical rotating speed for 18 hours, and drying at 80 ℃ for 4 hours to obtain powder;
s4, putting the powder in the step S3 into a die, extruding under the pressure of 220MPa, and drying at 40 ℃ for 4.5h to obtain a blank;
s5, performing discharge plasma sintering on the blank prepared in the step S4 under the condition of 1200 ℃ and 40MPa for 7min, discharging, cooling and blasting sand to prepare the tungsten steel ceramic hard alloy.
Example 4
Compared with the embodiment 3, the inhibitor is a mixture of TaC and TiC, and the mass ratio is 3: 1.85, and other conditions were not changed.
Example 5
Compared with example 3, the inhibitors are TaC and LaC2The mass ratio of the mixture of (1) to (3): 1.85, and other conditions were not changed.
Example 6
Compared with example 3, the inhibitors are TaC, TiC and LaC2The mass ratio of the mixture of (1) to (3): 0.5: 1.35, other conditions were not changed.
Example 7
Compared with example 3, the inhibitors are TaC, TiC and LaC2The mass ratio of the mixture of (1) to (3): 1.75: 0.1, and other conditions are not changed.
Comparative example 1
In comparison with example 3, the Fe-Si-Al oxide nanopowder was replaced by the Fe-Al oxide nanopowder prepared in comparative preparation example 1, and the other conditions were not changed.
Comparative example 2
In comparison with example 3, the Fe-Si-Al oxide nanopowder was replaced by the Fe-Si oxide nanopowder prepared in comparative preparation example 1, and the other conditions were not changed.
Comparative example 3
In comparison with example 3, the Fe-Si-Al oxide nanopowder was replaced by the Fe oxide nanopowder prepared in comparative preparation example 1, and other conditions were not changed.
Comparative example 4
Fe-Si-Al oxide nanopowder from porous SiO prepared in comparative preparation example 1, in comparison with example 32/Al2O3The hollow nano microspheres are replaced, and other conditions are not changed.
Comparative example 5
Compared with example 3, the discharge plasma sintering in step S5 was replaced with a normal sintering method, and other conditions were not changed.
The sintering method is that the mixture is put into a vacuum sintering furnace, the sintering temperature is 1450 ℃, and the temperature is kept for 60 min.
Test example 1
The tungsten steel ceramic hard alloy prepared in the examples 1 to 7 of the present invention and the comparative examples 1 to 5 was subjected to the performance test, and the results are shown in table 1.
TABLE 1
Wherein, the bending strength detection adopts ISO C test sample, test statistics. Rc-HV 30 XKICAnd is used for characterizing the crack resistance of the alloy.
From the above table, it can be seen that the tungsten steel ceramic hard alloy prepared in the embodiments 1 to 3 of the present invention has good comprehensive properties, good corrosion resistance, heat resistance, high temperature oxidation resistance, excellent wear resistance, good toughness, strength and bending resistance, high hardness, high density, fine and uniform structure, and wide application prospects.
Compared with the example 3, the inhibitor is only the mixture of TaC and TiC, so that the strength and the toughness of the hard alloy are reduced, and compared with the example 3, the inhibitor is TaC, TiC and LaC in the example 72The mass ratio of the mixture of (1) to (3): 1.75: 0.1, wherein, LaC2The content of (A) is low, so that the strength and the toughness of the hard alloy are slightly reduced. Lac2Segregation occurs at a WC/bonding phase interface, the interface energy is reduced, dissolved WC is prevented from being precipitated on the surface of a crystal grain, the rapid growth behavior of the WC crystal grain is inhibited, the introduction of structural defects such as pores and brittleness in the alloy is avoided, the growth of the crystal grain is inhibited, and therefore the strength, toughness and other properties of the hard alloy are improved. Example 5 in comparison to example 3, the inhibitors are only TaC and LaC2The hardness of the mixture (2) is lowered, the Rc value is lowered, and the strength is lowered. Example 6 in comparison to example 3, the inhibitors are TaC, TiC and LaC2The mass ratio of the mixture of (1) to (3): 0.5: 1.35, wherein the content of TiC is low. The hardness, the Rc value and the strength of the hard alloy are slightly reduced, the WC crystal grains are partially platy due to the addition of Ti, because titanium is partially gathered on an interface to change the interface, so that the shape of the WC crystal grains is greatly changed, and the partially platy WC hard alloy has higher hardness, better breakage resistance and thermal crack resistance, good plastic deformation resistance, less creep deformation and more excellent thermal deformation resistance. Thus, TaC and LaC are shown2And TiC has a synergistic effect.
In comparison with example 3, the Fe-Si-Al oxide nanopowder of comparative example 1 was substituted by the Fe-Al oxide nanopowder prepared in comparative preparation example 1, so that toughness and hardness of the cemented carbide were significantly reduced. The addition of Si forms second phase reinforcement, so that the bending strength and Vickers hardness of the alloy are improved; meanwhile, the prepared hard alloy has better corrosion resistance, heat resistance, high-temperature oxidation resistance, excellent abrasion resistance and better alloy toughness
Comparative example 2 compared with example 3, the Fe-Si-Al oxide nanopowder was replaced by the Fe-Si oxide nanopowder prepared in comparative preparation example 1, so that the strength, toughness, hardness, etc. of the cemented carbide were all decreased, and Al element and binder phase Ni formed gamma' -phase Ni during sintering3Al, and a gamma' phase (100 nm) can be fully precipitated in the binding phase through solution treatment and aging treatment, so that the alloy strengthening effect is realized, and the performance of the alloy is improved.
Comparative example 3 compared with example 3, the Fe-Si-Al oxide nanopowder was replaced by the Fe oxide nanopowder prepared in comparative preparation example 1, resulting in a decrease in strength, toughness, hardness, etc. of the cemented carbide and an uneven particle size distribution.
Comparative example 4 in comparison with example 3, Fe-Si-Al oxide nanopowder was prepared from the porous SiO obtained in comparative preparation example 12/Al2O3The hollow nano microspheres are used for replacing, so that the toughness and the Rc value of the hard alloy are reduced. In the iron-nickel binding phase, the fracture toughness of the hard alloy is improved by strengthening martensite phase transformation.
Compared with the embodiment 3, the comparative example 5 adopts the common sintering method to replace the spark plasma sintering in the step S5, so that the grain size distribution of the hard alloy is obviously uneven, the average grain size is increased, and the hard alloy prepared by the spark plasma sintering can obtain higher density and finer grain structure.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (8)
1. The preparation method of the tungsten steel ceramic hard alloy is characterized by comprising the following steps:
s1, uniformly mixing WC powder, Ni powder, Fe-Si-Al oxide nano powder and an inhibitor in a 97# gasoline medium to obtain a mixture;
s2, adding 97# gasoline as a medium into the mixture obtained in the step S1 for primary ball milling, and sieving the mixture through a 400-sand 500-mesh sieve to obtain mixed slurry;
s3, adding carboxymethyl cellulose serving as a forming agent into the mixed slurry obtained in the step S2, performing secondary ball milling, and performing primary drying to obtain powder;
s4, putting the powder in the step S3 into a die for extrusion, and drying for the second time to obtain a blank;
s5, performing discharge plasma sintering on the blank prepared in the step S4, discharging, cooling and sand blasting to prepare the tungsten steel ceramic hard alloy;
the preparation method of the Fe-Si-Al oxide nano powder comprises the following steps:
(1) porous SiO2/Al2O3Preparing hollow nano microspheres: dissolving aminosilane and aluminum isopropoxide in ethyl acetate to obtain an oil phase; dissolving a pore-foaming agent and a surfactant in water to obtain a water phase; adding the oil phase into the water phase, emulsifying, adjusting the pH value of the solution to 8-9, reacting for 7-12h, centrifuging, washing the solid, drying and calcining to obtain porous SiO2/Al2O3Hollow nano-microspheres;
(2) preparation of Fe-Si-Al oxide nanopowder: dissolving ferric nitrate in water, adding citric acid and the porous SiO prepared in the step (1)2/Al2O3Carrying out ultrasonic dispersion on hollow nano microspheres, and heating to 50-60 ℃ to evaporate a solvent to obtain sol; then raising the temperature to 180 ℃ and 200 ℃ and keeping the vacuum degree at 0.01-0.1MPa to form dry gel, taking out the dry gel, and igniting the dry gel to obtain Fe-Si-Al oxide nano powder;
the content of the pore-foaming agent in the water phase is 1-2 wt%; the content of the surfactant is 2-4 wt%;
the mass ratio of the aminosilane to the aluminum isopropoxide is (2-5): 10; the mass ratio of the citric acid to the ferric nitrate is (2-4): 1; the mass ratio of the ferric nitrate to the porous SiO2/Al2O3 hollow nano microsphere is 2: (3-5).
2. The method for preparing the tungsten steel ceramic hard alloy according to the claim 1, wherein the pore-foaming agent is selected from at least one of cetyl trimethyl ammonium bromide, ethylene oxide-propylene oxide triblock copolymer PEO20-PPO70-PEO20, PEO106-PPO70-PEO 106; the surfactant is selected from at least one of tween-80, tween-20, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium hexadecyl benzene sulfonate, sodium hexadecyl sulfate and sodium octadecyl sulfonate; the emulsification condition is that the emulsification is carried out for 3-5min at the rotating speed of 10000-; the calcination temperature is 400-500 ℃ and the time is 2-4 h.
3. The method for preparing the tungsten steel ceramic hard alloy according to claim 1, wherein the inhibitor is selected from TiC, VC, TaC and LaC2、Cr3C2At least one of (1).
4. The method for preparing the tungsten steel ceramic hard alloy according to claim 3, wherein the inhibitor is TaC, TiC and LaC2The mass ratio of the mixture of (1) to (3): (1-2): (0.2-0.5).
5. The method for preparing the tungsten steel ceramic hard alloy according to the claim 1, wherein the content of the WC powder is 82-90 wt%; the weight percentage content of the Ni powder is 7-12 wt%; the weight percentage content of the Fe-Si-Al oxide nano powder is 3-6 wt%; the weight percentage content of the inhibitor is 0.2-0.5 wt%.
6. The method for preparing tungsten steel ceramic hard alloy according to claim 1, wherein the solid-to-liquid ratio of the total mass of the WC powder, the Ni powder, the Fe-Si-Al oxide nanopowder and the inhibitor to 97# gasoline in step S1 is 1: (0.8-1.1) g/mL; the solid-liquid ratio of the mixture to 97# gasoline in the step S2 is 1: (0.4-0.6) g/mL; the first ball milling condition is that hard alloy balls with the diameter of 6-10mm are used as grinding bodies, and the ball-to-material ratio is (10-12): 1, ball milling rotation speed is 72-77% of critical rotation speed, and ball milling time is 36-48 h; in the step S3, the addition amount of the carboxymethyl cellulose is 2-3wt% of the mixed slurry; the conditions of the second ball milling are that hard alloy balls with the diameter of 6-10mm are used as grinding bodies, and the ball-to-material ratio is (7-10): 1, ball milling rotation speed is 70-74% of critical rotation speed, and ball milling time is 12-24 h; the first drying temperature is 70-85 ℃, and the time is 3-5 h; in the step S4, the extrusion pressure is 120-270MPa, the secondary drying temperature is 30-50 ℃, and the time is 4-5 h; the sintering condition of the discharge plasma in the step S5 is 1100-1300 ℃, and the discharge is performed for 5-10min under the pressure of 30-50 MPa.
7. The preparation method of the tungsten steel ceramic hard alloy according to claim 1, which is characterized by comprising the following steps:
s1, mixing 82-90wt% of WC powder, 7-12wt% of Ni powder, 3-6wt% of Fe-Si-Al oxide nano powder and 0.2-0.5wt% of inhibitor in a 97# gasoline medium in a mixer at 8000-10000r/min for 10-20min, wherein the total mass of the WC powder, the Ni powder, the Fe-Si-Al oxide nano powder and the inhibitor is 1: (0.8-1.1) g/mL to give a mixture;
wherein the inhibitor is TaC, TiC and LaC2The mass ratio of the mixture of (1) to (3): (1-2): (0.2-0.5);
s2, adding 97# gasoline into the mixture obtained in the step S1, wherein the solid-to-liquid ratio of the mixture to the 97# gasoline is 1: (0.4-0.6) g/mL, and performing ball milling under the conditions that hard alloy balls with the diameter of 6-10mm are adopted as grinding bodies, and the ball-to-material ratio is (10-12): 1, ball milling at the rotation speed of 72-77% of the critical rotation speed for 36-48h, and sieving the mixture through a 400-500-mesh sieve to obtain mixed slurry;
s3, adding carboxymethyl cellulose into the mixed slurry obtained in the step S2 to serve as a forming agent, wherein the addition amount of the carboxymethyl cellulose is 2-3wt% of the mixed slurry, and performing ball milling under the condition that hard alloy balls with the diameter of 6-10mm are adopted as grinding bodies, and the ball-to-material ratio is (7-10): 1, ball milling at 70-74% of critical speed for 12-24h, and drying at 70-85 ℃ for 3-5h to obtain powder;
s4, putting the powder in the step S3 into a die, extruding under the pressure of 120 and 270MPa, and drying at 30-50 ℃ for 4-5h to obtain a blank;
s5, performing discharge plasma sintering on the blank prepared in the step S4 under the conditions of 1100-1300 ℃ and 30-50MPa for 5-10min of discharge, discharging, cooling and sandblasting to prepare the tungsten steel ceramic hard alloy.
8. A tungsten steel ceramic cemented carbide produced by the production method according to any one of claims 1 to 7.
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