Hard alloy forming agent and preparation method and application thereof

Abstract

The invention discloses a hard alloy forming agent and a preparation method and application thereof. The hard alloy forming agent comprises an aliphatic hydrocarbon component and a carbonic ester component, the mass ratio of the aliphatic hydrocarbon component to the carbonic ester component is 1: 1-19: 1, and the carbonic ester component comprises aliphatic cyclic carbonic ester and / or aliphatic chain carbonic ester. The hard alloy forming agent is easy to sinter and remove, low in carbon residue and capable of effectively improving the structural performance of the hard alloy.

Description

Technical Field

[0001] The present application belongs to the technical field of cemented carbide preparation, and in particular relates to a cemented carbide forming agent and a preparation method and application thereof. Background Art

[0002] Cemented carbide has the excellent properties of high hardness and high toughness, and has become one of the most widely used products in powder metallurgy products in the world. With the continuous improvement of automation, in order to meet the efficiency of mechanical cutting and processing, the high-precision processing industry not only puts forward higher requirements on the comprehensive performance of cemented carbide tools, but also brings more difficulties to the molding of complex shaped products. Compared with traditional compression molding, injection molding, extrusion molding, and 3D printing technology are suitable for complex molding of cemented carbide, and the high-performance molding agent that matches it is the key technology of the molding process.

[0003] The existing cemented carbide forming agents are complex and difficult to form, which can easily lead to problems such as difficulty in carbon control and cracks in stress concentration areas of the cemented carbide, affecting the performance of the cemented carbide. Summary of the invention

[0004] The embodiments of the present application provide a cemented carbide forming agent, a preparation method and an application thereof. The cemented carbide forming agent of the present application is easy to sinter and remove, has low carbon residue, and can effectively improve the structural properties of cemented carbide.

[0005] In a first aspect, a cemented carbide forming agent includes an aliphatic hydrocarbon component and a carbonate component, wherein the mass ratio of the aliphatic hydrocarbon component to the carbonate component is 1:1 to 19:1, and the carbonate component includes an aliphatic cyclic carbonate and / or an aliphatic chain carbonate.

[0006] The cemented carbide forming agent provided in the embodiment of the present application has good wettability and formability with cemented carbide powder, and the cemented carbide forming agent provided in the embodiment of the present application is easy to sinter and remove, has low carbon residue, and the sintering gas is non-toxic and environmentally friendly, and has excellent comprehensive performance.

[0007] Moreover, when the mass ratio of the aliphatic hydrocarbon component to the carbonate component is 1:1 to 19:1, on the one hand, the cemented carbide forming agent provided in the embodiment of the present application can be well adsorbed on the surface of the cemented carbide powder particles, thereby enhancing the bonding force between the powders, helping to form a stable green body during the pressing process and reducing the breakage of the green body. On the other hand, when the cemented carbide forming agent provided in the embodiment of the present application is mixed with the cemented carbide powder, the powder can flow and fill the mold more easily, thereby improving the efficiency and precision of the molding, and is particularly suitable for preparing cemented carbide products of complex shapes.

[0008] In a first possible implementation, the aliphatic cyclic carbonate is prepared from an aliphatic diol having 2 to 8 carbon atoms. Optionally, the structure of the cyclic carbonate is as shown in formula (I) and / or formula (II):

[0009]

[0010] Among them, R1, R2, R3, and R4 are hydrogen atoms or aliphatic hydrocarbon groups with a carbon number of ≤6, and the sum of the carbon numbers of R1, R2, R3, and R4 is ≤6, R5 is an aliphatic hydrocarbon group with a carbon number of ≤6, R6, R7, R8, and R9 are hydrogen atoms or aliphatic hydrocarbon groups with a carbon number of ≤5, and the sum of the carbon numbers of R5, R6, R7, R8, and R9 is ≤6.

[0011] The cemented carbide forming agent provided in the embodiment of the present application adopts the above-mentioned aliphatic cyclic carbonate, and the decomposition temperature of the cemented carbide forming agent matches the sintering temperature of the cemented carbide, and can be well connected with the sintering process during the degreasing process. In addition, the aliphatic cyclic carbonate can dissolve the carbon deposits generated by the components in the cemented carbide forming agent at high temperatures during the cemented carbide production process, further reducing the carbon residue in the cemented carbide.

[0012] In combination with the above possible embodiments, one branch of the aliphatic chain carbonate is prepared from an aliphatic monohydric alcohol having 1 to 8 carbon atoms, and the other branch is prepared from an aliphatic monohydric alcohol having 2 to 8 carbon atoms. Optionally, the structure of the aliphatic chain carbonate is shown in formula (III):

[0013]

[0014] Among them, R 10 and R 11 are all aliphatic hydrocarbon groups with ≤8 carbon atoms, and R 10 and R 11 The sum of the number of carbon atoms is between 3 and 16.

[0015] The cemented carbide forming agent provided in the embodiment of the present application adopts the above-mentioned aliphatic chain carbonate. The cemented carbide forming agent has better fluidity, can make the cemented carbide powder better fill and distribute in the mold, reduce the pressing pressure, and improve the forming efficiency. It is particularly suitable for preparing cemented carbide products with complex shapes, and can obtain a green body with smooth surface and high dimensional accuracy.

[0016] In combination with the above possible embodiments, the aliphatic chain carbonate is an aliphatic chain ether alcohol carbonate, one branch of the aliphatic chain ether alcohol carbonate is prepared from an aliphatic ether alcohol containing 1 hydroxyl group, 1 to 4 ether bonds, ether bonds and end-capped ether bonds connecting a hydrocarbon group with 1 to 5 carbon atoms, and the other branch is obtained by reacting an aliphatic ether alcohol having 1 hydroxyl group, 1 to 4 ether bonds, ether bonds and end-capped ether bonds connecting a hydrocarbon group with 1 to 5 carbon atoms or an aliphatic monohydric alcohol with 1 to 8 carbon atoms. Optionally, the structural formula of the aliphatic chain ether alcohol carbonate is shown in formula (IV) and / or formula (V):

[0017]

[0018] Among them, R 12 , R 13 , R 14 , R 15 It is an aliphatic hydrocarbon group having 5 or less carbon atoms, and m and n are integers of 1 to 4.

[0019] The cemented carbide forming agent provided by the embodiment of the present application adopts the above-mentioned aliphatic chain ether alcohol carbonate, and the cemented carbide forming agent contains more oxygen elements, and the oxygen atoms can form coordination bonds or hydrogen bonds with the metal ions or other active sites on the surface of the cemented carbide powder, so as to enhance the bonding force between the forming agent and the powder particles, so that the blank is less likely to break during pressing and handling, and it is helpful to improve the strength and quality of the blank. At the same time, the presence of oxygen elements can increase the polarity of the chain ether alcohol carbonate molecule, so that it has better fluidity at a certain temperature and pressure, and can better fill every corner of the mold, so that the cemented carbide powder is distributed more evenly in the mold, which is conducive to improving the molding efficiency and the density uniformity of the blank. In addition, higher oxygen content helps the cemented carbide forming agent to escape in the form of CO2 during the cemented carbide molding process.

[0020] In combination with the above possible embodiments, the aliphatic cyclic carbonate is modified from a rubber-type hard alloy forming agent and / or a polyethylene glycol-type hard alloy forming agent; and / or, the aliphatic chain carbonate is modified from a rubber-type hard alloy forming agent and / or a polyethylene glycol-type hard alloy forming agent. Optionally, the aliphatic chain carbonate is an aliphatic chain ether alcohol carbonate, and the aliphatic chain ether alcohol carbonate is modified from a rubber-type hard alloy forming agent and / or a polyethylene glycol-type hard alloy forming agent.

[0021] In combination with the above possible embodiments, the carbonate component includes aliphatic cyclic carbonate and aliphatic chain ether alcohol carbonate, and the mass ratio of aliphatic chain ether alcohol carbonate to aliphatic cyclic carbonate is ≥ 1. At this mass ratio, aliphatic chain ether alcohol carbonate and aliphatic cyclic carbonate act synergistically, on the one hand, aliphatic cyclic carbonate reduces carbon deposits, and on the other hand, aliphatic chain ether alcohol carbonate improves carbon deposit oxidation removal, and carbon residues in cemented carbide are lower.

[0022] In combination with the above possible embodiments, the aliphatic hydrocarbon component is one or more aliphatic hydrocarbon compounds having carbon atoms of 8 to 30. Optionally, the aliphatic hydrocarbon component is one or more aliphatic hydrocarbon compounds having carbon atoms of 10 to 15, and further optionally, the aliphatic hydrocarbon component is one of aliphatic hydrocarbon compounds having carbon atoms of 10 to 15.

[0023] In combination with the above possible embodiments, the aliphatic hydrocarbon component is an aliphatic alkane mixture.

[0024] In combination with the above possible embodiments, the amount of cemented carbide forming agent used is 3% to 6% of the mass of the cemented carbide powder.

[0025] In the embodiment of the present application, the amount of cemented carbide forming agent used is 5.5% to 6% of the mass of cemented carbide powder. In the degreasing process of cemented carbide preparation, the removal efficiency of the cemented carbide forming agent can be improved, and the residual carbon generated by incomplete degreasing can be reduced. At the same time, the steam pressure generated by the cemented carbide forming agent during the volatilization process is relatively moderate, ensuring that the green body still maintains good structural integrity after degreasing, providing guarantee for subsequent sintering and the performance of the final product.

[0026] In combination with the above possible embodiments, the cemented carbide forming agent satisfies at least one of the following: (1) the viscosity of the cemented carbide forming agent at 25°C is 1 cp to 35 cp; (2) the surface tension of the cemented carbide forming agent is 20 mN / m to 40 mN / m; (3) the friction coefficient of the cemented carbide forming agent is 0.05 to 0.15.

[0027] In a second aspect, an embodiment of the present application provides a method for preparing a cemented carbide forming agent, wherein an aliphatic hydrocarbon component and a carbonate component are uniformly mixed in a mass ratio of 1:1 to 19:1 to obtain a cemented carbide forming agent, wherein the carbonate component is one or more of an aliphatic cyclic carbonate, an aliphatic chain carbonate, and an aliphatic chain ether alcohol carbonate.

[0028] In a third aspect, an embodiment of the present application provides a cemented carbide, which is prepared by the cemented carbide forming agent prepared by the first aspect and / or the cemented carbide forming agent prepared by the preparation method of the second aspect.

[0029] The cemented carbide provided in the embodiments of the present application has the advantages of few structural defects, not prone to cracks, and high stock strength. DETAILED DESCRIPTION

[0030] The features and exemplary embodiments of various aspects of the present application will be described in detail below. In order to make the purpose, technical solutions and advantages of the present application clearer, the present application will be further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only intended to explain the present application, rather than to limit the present application. For those skilled in the art, the present application can be implemented without the need for some of these specific details. The following description of the embodiments is only to provide a better understanding of the present application by illustrating the examples of the present application.

[0031] For simplicity, this application only explicitly discloses some numerical ranges. However, any lower limit can be combined with any upper limit to form an unclearly recorded range; and any lower limit can be combined with other lower limits to form an unclearly recorded range, and any upper limit can be combined with any other upper limit to form an unclearly recorded range. In addition, although not clearly recorded, each point or single value between the range endpoints is included in the range. Thus, each point or single value can be combined with any other point or single value as its own lower limit or upper limit or with other lower limits or upper limits to form an unclearly recorded range.

[0032] The above-mentioned inventive content of the present application is not intended to describe each disclosed embodiment or each implementation in the present application. The following description more specifically illustrates an exemplary embodiment. In many places throughout the application, guidance is provided by a series of embodiments, which can be used in various combinations. In each example, the enumeration is only a representative group and should not be interpreted as exhaustive. In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be understood as indicating or implying relative importance or implicitly indicating the number of indicated technical features. Thus, the features defined as "first" and "second" can explicitly or implicitly include at least one of the features. In the description of the present application, the meaning of "multiple" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0033] It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application may be combined with each other.

[0034] In addition, the term "and / or" in this article is only a description of the association relationship between the associated objects, indicating that there can be three relationships. For example, A and / or B can represent: A exists alone, A and B exist at the same time, and B exists alone. In addition, the character " / " in this article generally indicates that the associated objects before and after are in an "or" relationship.

[0035] It should be understood that in the embodiment of the present application, "B corresponding to A" means that B is associated with A, and B can be determined according to A. However, it should also be understood that determining B according to A does not mean determining B only according to A, and B can also be determined according to A and / or other information.

[0036] Cemented carbide has the excellent properties of high hardness and high toughness, and has become one of the most widely used products in powder metallurgy products in the world. With the continuous improvement of automation, in order to meet the efficiency of mechanical cutting and processing, the high-precision processing industry not only puts forward higher requirements on the comprehensive performance of cemented carbide tools, but also brings more difficulties to the molding of complex shaped products. Compared with traditional compression molding, injection molding, extrusion molding, and 3D printing technology are suitable for complex molding, and the high-performance cemented carbide molding agent that matches them is the key technology of the molding process.

[0037] Cemented carbide forming agent is an auxiliary raw material in the production process of cemented carbide powder metallurgy. It plays a role in improving the powder forming performance, can maintain powder infiltration, improve green strength, reduce friction, promote particle rearrangement, and increase powder plasticity.

[0038] At present, the three types of cemented carbide forming agents widely used are rubber, paraffin and polyethylene glycol. Rubber cemented carbide forming agents have large molecular weight, wide distribution, high carbon residue, and difficult to accurately control carbon. Paraffin cemented carbide forming agents can be completely volatilized at high temperature, easy to remove, no residue, and reduce the difficulty of carbon control, but they have low viscosity, low strength of the blank, easy to fall off, large elastic aftereffect, and stress concentration parts are prone to cracks, making it difficult to process products with complex shapes. Polyethylene glycol cemented carbide forming agents also have less residual carbon, but they absorb moisture severely, and the molding pressure increases after moisture absorption, making complex molding more difficult.

[0039] In view of the above technical problems, the embodiments of the present application provide a cemented carbide forming agent and a preparation method and application thereof. The cemented carbide forming agent of the present application is easy to sinter and remove, has low carbon residue, and effectively reduces the structural defects of cemented carbide.

[0040] The cemented carbide forming agent provided in this application is introduced below.

[0041] In a first aspect, a cemented carbide forming agent includes an aliphatic hydrocarbon component and a carbonate component, wherein the mass ratio of the aliphatic hydrocarbon component to the carbonate component is 1:1 to 19:1, and the carbonate component includes an aliphatic cyclic carbonate and / or an aliphatic chain carbonate.

[0042] For example, the mass ratio of the aliphatic hydrocarbon component to the carbonate component can be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, or a range consisting of any of the above values.

[0043] The cemented carbide forming agent provided in the embodiment of the present application has good wettability and formability with cemented carbide powder, and the cemented carbide forming agent of the present application is easy to sinter and remove, has low carbon residue, and the sintering gas is non-toxic and environmentally friendly, and has excellent comprehensive performance.

[0044] Moreover, when the mass ratio of the aliphatic hydrocarbon component to the carbonate component is 1:1 to 19:1, on the one hand, the cemented carbide forming agent provided in the embodiment of the present application can be well adsorbed on the surface of the cemented carbide powder particles, thereby enhancing the bonding force between the powders, helping to form a stable green body during the pressing process and reducing the breakage of the green body. On the other hand, when the cemented carbide forming agent provided in the embodiment of the present application is mixed with the cemented carbide powder, the powder can flow and fill the mold more easily, thereby improving the efficiency and precision of the molding, and is particularly suitable for preparing cemented carbide products of complex shapes.

[0045] In some embodiments, the aliphatic cyclic carbonate is prepared from an aliphatic diol having 2 to 8 carbon atoms. For example, the aliphatic diol may have 2, 3, 4, 5, 6, 7, or 8 carbon atoms. Optionally, the structure of the cyclic carbonate is as shown in formula (I) and / or formula (II):

[0046]

[0047] Among them, R1, R2, R3, and R4 are hydrogen atoms or aliphatic hydrocarbon groups with a carbon number of ≤6, for example, R1, R2, R3, and R4 can all be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, vinyl, propenyl, etc., and the sum of the carbon numbers of R1, R2, R3, and R4 is ≤6, for example, the sum of the carbon numbers of R1, R2, R3, and R4 can be 3, 4, 5, or 6; R5 is an aliphatic hydrocarbon group with a carbon number of ≤6, for example, R5 The number of carbon atoms can be 2, 3, 4, 5, or 6, and R6, R7, R8, and R9 are hydrogen atoms or aliphatic hydrocarbon groups with a carbon number ≤5. For example, R5, R6, R7, R8, and R9 can all be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, vinyl, and propenyl groups, and the sum of the carbon numbers of R5, R6, R7, R8, and R9 is ≤6. For example, the sum of the carbon numbers of R5, R6, R7, R8, and R9 can be 3, 4, 5, or 6.

[0048] In the embodiment of the present application, the above-mentioned aliphatic cyclic carbonate is used, and the decomposition temperature of the cemented carbide forming agent matches the sintering temperature of the cemented carbide, and the degreasing process can be well connected with the sintering process. In addition, the aliphatic cyclic carbonate can dissolve the carbon deposits generated by the components in the cemented carbide forming agent at high temperatures during the cemented carbide production process, further reducing the carbon residue in the cemented carbide.

[0049] In some embodiments, one branch of the aliphatic chain carbonate is prepared from an aliphatic monohydric alcohol having 1 to 8 carbon atoms, for example, the carbon atoms of the aliphatic monohydric alcohol can be 1, 2, 3, 4, 5, 6, 7, 8; the other branch is prepared from an aliphatic monohydric alcohol having 2 to 8 carbon atoms, for example, the carbon atoms of the aliphatic monohydric alcohol can be 2, 3, 4, 5, 6, 7, 8. Optionally, the structure of the aliphatic chain carbonate is shown in formula (III):

[0050]

[0051] Wherein, R10 and R11 are both aliphatic hydrocarbon groups with carbon atoms ≤ 8, and the sum of the carbon atoms of R10 and R11 is between 3 and 16.

[0052] In the embodiments of the present application, the above-mentioned aliphatic chain carbonate is used, and the cemented carbide forming agent has better fluidity, which can make the cemented carbide powder better filled and distributed in the mold, reduce the pressing pressure, and improve the forming efficiency. It is particularly suitable for preparing cemented carbide products with complex shapes, and can obtain a green body with a smooth surface and high dimensional accuracy.

[0053] In some embodiments, the aliphatic chain carbonate is an aliphatic chain ether alcohol carbonate, and one branch of the aliphatic chain ether alcohol carbonate is prepared from an aliphatic ether alcohol containing 1 hydroxyl group, 1 to 4 ether bonds, ether bonds and end-capped ether bonds connecting a hydrocarbon group with 1 to 5 carbon atoms. For example, the number of ether bonds of the aliphatic ether alcohol can be 1, 2, 3, or 4, and the number of carbon atoms connected by the end-capped ether bonds can be 1, 2, 3, 4, or 5; the other branch is obtained by reacting an aliphatic ether alcohol having 1 hydroxyl group, 1 to 4 ether bonds, ether bonds and end-capped ether bonds connecting a hydrocarbon group with 1 to 5 carbon atoms or an aliphatic monohydric alcohol with 1 to 8 carbon atoms. Optionally, the structural formula of the aliphatic chain ether alcohol carbonate is shown in formula (IV) and / or formula (V):

[0054]

[0055]

[0056] Among them, R12, R13, R14, and R15 are aliphatic hydrocarbon groups with carbon atoms ≤ 5, and m and n are integers of 1 to 4.

[0057] In the present application embodiment, the above-mentioned aliphatic chain ether alcohol carbonate is used, and the cemented carbide forming agent contains more oxygen elements, and the oxygen atoms can form coordination bonds or hydrogen bonds with the metal ions or other active sites on the surface of the cemented carbide powder, thereby enhancing the bonding force between the forming agent and the powder particles, making the blank less likely to break during pressing and handling, and helping to improve the strength and quality of the blank. At the same time, the presence of oxygen elements can increase the polarity of the chain ether alcohol carbonate molecule, so that it has better fluidity at a certain temperature and pressure, can better fill every corner of the mold, and make the cemented carbide powder more evenly distributed in the mold, which is conducive to improving the molding efficiency and the density uniformity of the blank. In addition, higher oxygen content helps the cemented carbide forming agent to escape in the form of CO2 during the cemented carbide molding process.

[0058] In some embodiments, the aliphatic cyclic carbonate is modified from a rubber-type hard alloy forming agent and / or a polyethylene glycol-type hard alloy forming agent; and / or, the aliphatic chain carbonate is modified from a rubber-type hard alloy forming agent and / or a polyethylene glycol-type hard alloy forming agent, optionally, the aliphatic chain carbonate is an aliphatic chain ether alcohol carbonate, and the aliphatic chain ether alcohol carbonate is modified from a rubber-type hard alloy forming agent and / or a polyethylene glycol-type hard alloy forming agent.

[0059] In some embodiments, the carbonate component includes aliphatic cyclic carbonate and aliphatic chain ether alcohol carbonate, and the mass ratio of aliphatic chain ether alcohol carbonate to aliphatic cyclic carbonate is ≥1, for example, the mass ratio of aliphatic chain ether alcohol carbonate to aliphatic cyclic carbonate can be 1, 1.2, 1.5, 1.8, 2, 3, 4 or the range of any of the above numerical values. At this mass ratio, aliphatic chain ether alcohol carbonate and aliphatic cyclic carbonate work synergistically, on the one hand, aliphatic cyclic carbonate reduces carbon deposition, on the other hand, aliphatic chain ether alcohol carbonate improves carbon deposition oxidation removal, and carbon residue in cemented carbide is lower.

[0060] In some embodiments, the aliphatic hydrocarbon component is one or more aliphatic hydrocarbon compounds with 8 to 30 carbon atoms, for example, the carbon atoms of the aliphatic hydrocarbon compounds can be 8, 9, 10, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30. Optionally, the aliphatic hydrocarbon component is one or more aliphatic hydrocarbon compounds with 10 to 15 carbon atoms, and further optionally, the aliphatic hydrocarbon component is one of the aliphatic hydrocarbon compounds with 10 to 15 carbon atoms. The aliphatic hydrocarbon component is one of the aliphatic hydrocarbon compounds with 10 to 15 carbon atoms, and the aliphatic hydrocarbon compounds with this carbon number have good physical properties and volatility, which is helpful for the quality control of the cemented carbide forming agent and the removal of the cemented carbide forming agent in the subsequent cemented carbide preparation process.

[0061] In some embodiments, the aliphatic hydrocarbon component is an aliphatic alkane mixture. For example, the aliphatic alkane mixture includes aliphatic alkanes of different carbon chain lengths, from shorter carbon chains such as propane containing 3 carbon atoms, to medium-length carbon chains, such as octane containing 8 carbon atoms, and even longer carbon chain alkanes. The aliphatic alkanes may be derived from the distillation process of petroleum, and fractions containing different proportions of aliphatic alkanes can be obtained at different distillation stages; they may also be prepared by specific organic synthesis reactions.

[0062] In some embodiments, the amount of cemented carbide forming agent is 3% to 6% of the mass of cemented carbide powder, for example, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, or a range consisting of any of the above values.

[0063] In the embodiment of the present application, the amount of cemented carbide forming agent used is 5.5% to 6% of the mass of cemented carbide powder. In the degreasing process of cemented carbide preparation, the removal efficiency of the cemented carbide forming agent can be improved, and the residual carbon generated by incomplete degreasing can be reduced. At the same time, the steam pressure generated by the cemented carbide forming agent during the volatilization process is relatively moderate, ensuring that the green body still maintains good structural integrity after degreasing, providing guarantee for subsequent sintering and the performance of the final product.

[0064] In some embodiments, the cemented carbide forming agent satisfies at least one of the following: (1) the viscosity of the cemented carbide forming agent at 25° C. is 1 cp to 35 cp, for example, 1 cp, 5 cp, 10 cp, 15 cp, 20 cp, 25 cp, 30 cp, 35 cp, or a range consisting of any of the above values; (2) the surface tension of the cemented carbide forming agent is 20 mN / m to 40 mN / m, for example, 20 mN / m, 21 mN / m, 22 mN / m, 23 mN / m, 24 mN / m, 25 mN / m, 26 mN / m, 27 mN / m, 28 mN / m, 29 mN / m, 30 mN / m, 31 mN / m, 32 mN / m, 33 mN / m, 34 mN / m, 35 mN / m, 36 mN / m, 37 mN / m, 38 mN / m, 39 mN / m, 40 mN / m, 41 mN / m, 42 mN / m, 43 mN / m, 44 mN / m, 45 mN / m, 46 mN / m, 47 mN / m, 48 mN / m, 49 mN / m, 50 mN / m, 51 mN / m, 52 mN / m, 53 mN / m, 54 mN / m, 55 mN / m, 56 mN / m, 57 mN / m, 58 mN / m, 59 mN / m, 60 mN / m, 61 mN / m, 62 mN / m, 63 mN / m, 64 mN / m, 8mN / m, 29mN / m, 30mN / m, 31mN / m, 32mN / m, 33mN / m, 34mN / m, 35mN / m, 36mN / m, 37mN / m, 38mN / m, 39mN / m, 40mN / m, or a range consisting of any of the above values; (3) the friction coefficient of the cemented carbide forming agent is 0.05 to 0.15, for example, it can be 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, or a range consisting of any of the above values.

[0065] In a second aspect, an embodiment of the present application provides a method for preparing a cemented carbide forming agent, wherein an aliphatic hydrocarbon component and a carbonate component are uniformly mixed in a mass ratio of 1:1 to 19:1 to obtain a cemented carbide forming agent, wherein the carbonate component is one or more of an aliphatic cyclic carbonate, an aliphatic chain carbonate, and an aliphatic chain ether alcohol carbonate.

[0066] In a third aspect, an embodiment of the present application provides a cemented carbide, which is prepared by the cemented carbide forming agent prepared by the first aspect and / or the cemented carbide forming agent prepared by the preparation method of the second aspect. Optionally, the cemented carbide can be a solid rod formed by extrusion or a rod with internal cooling holes.

[0067] The cemented carbide provided in the embodiments of the present application has the advantages of few structural defects, not prone to cracks, and high stock strength.

[0068] The following examples describe the present disclosure in more detail, and these examples are intended for illustrative purposes only.

[0069] Because various modifications and variations are obvious to those skilled in the art within the scope of the present disclosure. Unless otherwise stated, all parts, percentages and ratios reported in the following examples are based on mass, and all raw materials used in the examples are commercially available or prepared according to conventional methods and can be used directly without further treatment, and the instruments used in the examples are commercially available.

[0070] The cemented carbide powder used in this embodiment includes a cemented compound tungsten carbide powder and a bonding metal cobalt.

[0071] Example 1

[0072] A cemented carbide forming agent includes an aliphatic hydrocarbon component and a carbonate component, wherein the mass ratio of the aliphatic hydrocarbon component to the carbonate component is 5:1, wherein the cemented carbide forming agent is obtained by mixing the aliphatic hydrocarbon component including 1000g of an alkane mixture having carbon atoms of 8 to 18 and 200g of an aliphatic chain carbonate having carbon atoms of 4 to 8. The cemented carbide forming agent of this embodiment has a viscosity of 1.83cp at 25°C, a surface tension of 25.85mN / m, and a friction coefficient of 0.13.

[0073] A cemented carbide rod is formed by extrusion, wherein the raw material includes 6wt% of the above-mentioned cemented carbide forming agent, the extrusion pressure is 100MPa to 200MPa, the extrusion is smooth without cracks, there is no cobalt pool after sintering, the metallographic phase is normal, and the carbon residue is 0.5%

[0074] Example 2

[0075] A cemented carbide forming agent comprises an aliphatic hydrocarbon component and a carbonate component, wherein the mass ratio of the aliphatic hydrocarbon component to the carbonate component is 2.5:1, wherein the cemented carbide forming agent is obtained by mixing the aliphatic hydrocarbon component with 1000g of an alkane mixture having 8 to 16 carbon atoms, 250g of an aliphatic chain carbonate having 3 to 6 carbon atoms, and 150g of a mixture of methyl (methoxyethyl) carbonate and methyl (ethoxyethyl) carbonate. The cemented carbide forming agent of this embodiment has a viscosity of 1.77cp at 25°C, a surface tension of 26.1mN / m, and a friction coefficient of 0.107.

[0076] A cemented carbide rod is formed by extrusion. The raw material includes 6wt% of the cemented carbide forming agent. The extrusion pressure is 100MPa-200MPa. The extrusion is smooth without cracks. After sintering, there is no cobalt pool, no metallographic abnormality, and the carbon residue is 0.37%.

[0077] Example 3

[0078] A cemented carbide forming agent comprises an aliphatic hydrocarbon component and a carbonate component, wherein the mass ratio of the aliphatic hydrocarbon component to the carbonate component is 3.33:1, wherein the cemented carbide forming agent is obtained by mixing the aliphatic hydrocarbon component with 1000g of an alkane mixture having 8 to 16 carbon atoms, 100g of an aliphatic cyclic carbonate mixture having 3 to 6 carbon atoms, and 100g of methyl (methoxyethyl) carbonate and methyl (ethoxyethyl) carbonate mixture. The cemented carbide forming agent of this embodiment has a viscosity of 1.27cp at 25°C, a surface tension of 26.34mN / m, and a friction coefficient of 0.083.

[0079] A cemented carbide rod is formed by extrusion. The raw material includes 5.5wt% of the cemented carbide forming agent. The extrusion pressure is 100MPa-200MPa. The extrusion is smooth without cracks. After sintering, there is no cobalt pool, no metallographic abnormality, and the carbon residue is 0.26%.

[0080] Example 4

[0081] A cemented carbide forming agent comprises an aliphatic hydrocarbon component and a carbonate component, wherein the mass ratio of the aliphatic hydrocarbon component to the carbonate component is 9:1, wherein the cemented carbide forming agent is obtained by mixing 900g of an aliphatic hydrocarbon having 15 carbon atoms, 50g of an aliphatic cyclic carbonate mixture having 3 to 6 carbon atoms, and 50g of a mixture of methyl (methoxyethyl) carbonate and methyl (ethoxyethyl) carbonate. The cemented carbide forming agent of this embodiment has a viscosity of 2.36cp at 25°C, a surface tension of 28.15mN / m, and a friction coefficient of 0.082.

[0082] A cemented carbide rod is formed by extrusion. The raw material includes 5.5wt% of the cemented carbide forming agent. The extrusion pressure is 100MPa-200MPa. The extrusion is smooth without cracks. After sintering, there is no cobalt pool, no metallographic abnormality, and the carbon residue is 0.17%.

[0083] Comparative Example 1

[0084] A cemented carbide forming agent comprises an aliphatic hydrocarbon component and a carbonate component, wherein the mass ratio of the aliphatic hydrocarbon component to the carbonate component is 1:2, wherein the cemented carbide forming agent is obtained by mixing the aliphatic hydrocarbon component with 400 g of an alkane mixture having carbon atoms of 8 to 18 and 800 g of an aliphatic chain carbonate having carbon atoms of 4 to 8. The cemented carbide forming agent of this comparative example has a viscosity of 1.58 cp at 25° C., a surface tension of 28.22 mN / m, and a friction coefficient of 0.12.

[0085] A cemented carbide rod is formed by extrusion, wherein the raw material comprises 5.5wt% of the cemented carbide forming agent, the extrusion pressure is 100MPa-200MPa, and the carbon residue is 0.89%.

[0086] Comparative Example 2

[0087] A cemented carbide forming agent comprises an aliphatic hydrocarbon component and a carbonate component, wherein the mass ratio of the aliphatic hydrocarbon component to the carbonate component is 24:1, wherein the cemented carbide forming agent is obtained by mixing the aliphatic hydrocarbon component with 1200 g of an alkane mixture having carbon atoms of 8 to 18 and 50 g of an aliphatic chain carbonate having carbon atoms of 4 to 8. The cemented carbide forming agent of this comparative example has a viscosity of 2.12 cp at 25° C., a surface tension of 24.86 mN / m, and a friction coefficient of 0.101.

[0088] A cemented carbide rod is formed by extrusion, wherein the raw material comprises 5.5wt% of the cemented carbide forming agent, the extrusion pressure is 100MPa-200MPa, and the carbon residue is 0.96%.

[0089] Comparative Example 3

[0090] The existing cemented carbide forming agent (alkanes with carbon atoms of 8 to 18) is used. A cemented carbide rod is formed by extrusion, wherein the raw material includes 5.5 wt% of the above cemented carbide forming agent, the extrusion pressure is 100 MPa to 200 MPa, and the carbon residue is 1.13%.

[0091] The above is only a specific implementation of the present application, but the protection scope of the present application is not limited thereto. Any technician familiar with the technical field can easily think of various equivalent modifications or replacements within the technical scope disclosed in the present application, and these modifications or replacements should be included in the protection scope of the present application. Therefore, the protection scope of the present application shall be based on the protection scope of the claims.

Claims

1. A cemented carbide forming agent, characterized in that: The invention comprises an aliphatic hydrocarbon component and a carbonate component, wherein the mass ratio of the aliphatic hydrocarbon component to the carbonate component is 1:1 to 19:1, and the carbonate component comprises an aliphatic cyclic carbonate and / or an aliphatic chain carbonate.

2. The cemented carbide forming agent according to claim 1, characterized in that: The aliphatic cyclic carbonate is prepared from an aliphatic diol having 2 to 8 carbon atoms. Preferably, the structure of the aliphatic cyclic carbonate is as shown in formula (I) and / or formula (II): Among them, R1, R2, R3, and R4 are hydrogen atoms or aliphatic hydrocarbon groups with a carbon number of ≤6, and the sum of the carbon numbers of R1, R2, R3, and R4 is ≤6, R5 is an aliphatic hydrocarbon group with a carbon number of ≤6, R6, R7, R8, and R9 are hydrogen atoms or aliphatic hydrocarbon groups with a carbon number of ≤5, and the sum of the carbon numbers of R5, R6, R7, R8, and R9 is ≤6.

3. The cemented carbide forming agent according to claim 1, characterized in that: One branch of the aliphatic chain carbonate is prepared from an aliphatic monohydric alcohol having 1 to 8 carbon atoms, and the other branch is prepared from an aliphatic monohydric alcohol having 2 to 8 carbon atoms. Preferably, the structure of the aliphatic chain carbonate is shown in formula (III): Among them, R 10 and R 11 are all aliphatic hydrocarbon groups with carbon atoms ≤ 8, and R 10 and R 11 The sum of the number of carbon atoms is between 3 and 16.

4. The cemented carbide forming agent according to claim 1, characterized in that: The aliphatic chain carbonate is an aliphatic chain ether alcohol carbonate, one branch of which is prepared from an aliphatic ether alcohol containing 1 hydroxyl group, 1 to 4 ether bonds, ether bonds and end-capped ether bonds connecting a hydrocarbon group with 1 to 5 carbon atoms, and the other branch is obtained by reacting an aliphatic ether alcohol containing 1 hydroxyl group, 1 to 4 ether bonds, ether bonds and end-capped ether bonds connecting a hydrocarbon group with 1 to 5 carbon atoms or an aliphatic monohydric alcohol with 1 to 8 carbon atoms. Preferably, the structural formula of the aliphatic chain ether alcohol carbonate is as shown in formula (IV) and / or formula (V): Among them, R 12 , R 13 , R 14 , R 15 It is an aliphatic hydrocarbon group having 5 or less carbon atoms, and m and n are integers of 1 to 4.

5. The cemented carbide forming agent according to claim 1, characterized in that: The aliphatic cyclic carbonate is obtained by modifying a glue-based hard alloy forming agent and / or a polyethylene glycol-based hard alloy forming agent; And / or, the aliphatic chain carbonate is modified from a rubber-based cemented carbide forming agent and / or a polyethylene glycol-based cemented carbide forming agent. Preferably, the aliphatic chain carbonate is an aliphatic chain ether alcohol carbonate, which is modified from a rubber-based cemented carbide forming agent and / or a polyethylene glycol-based cemented carbide forming agent.

6. The cemented carbide forming agent according to claim 1, characterized in that: The carbonate component comprises an aliphatic cyclic carbonate and an aliphatic chain ether alcohol carbonate, and the mass ratio of the aliphatic chain ether alcohol carbonate to the aliphatic cyclic carbonate is ≥1.

7. The cemented carbide forming agent according to claim 1, characterized in that: The aliphatic hydrocarbon component is one or more aliphatic hydrocarbon compounds having 8 to 30 carbon atoms. Preferably, the aliphatic hydrocarbon component is one or more aliphatic hydrocarbon compounds having 10 to 15 carbon atoms. More preferably, the aliphatic hydrocarbon component is one of the aliphatic hydrocarbon compounds having 10 to 15 carbon atoms.

8. The cemented carbide forming agent according to claim 1, characterized in that: The aliphatic hydrocarbon component is an aliphatic alkane mixture.

9. The cemented carbide forming agent according to claim 1, characterized in that: The usage of the cemented carbide forming agent is 3% to 6% of the mass of the cemented carbide powder.

10. The cemented carbide forming agent according to any one of claims 1 to 9, characterized in that: The cemented carbide forming agent satisfies at least one of the following: (1) The viscosity of the cemented carbide forming agent at 25° C. is 1 cp to 35 cp; (2) The surface tension of the cemented carbide forming agent is 20 mN / m to 40 mN / m; (3) The friction coefficient of the cemented carbide forming agent is 0.05 to 0.

15.

11. A method for preparing a cemented carbide forming agent, characterized in that: The cemented carbide forming agent is obtained by uniformly mixing an aliphatic hydrocarbon component and a carbonate component at a mass ratio of 1:1 to 19:1, wherein the carbonate component includes an aliphatic cyclic carbonate and / or an aliphatic chain carbonate.

12. A cemented carbide, characterized in that: The hard alloy forming agent is prepared by the hard alloy forming agent according to any one of claims 1 to 10 and / or prepared by the preparation method according to claim 11.

Images