CN109231211B - Method for preparing ultrafine tungsten carbide powder by taking tungsten powder and glucose as raw materials - Google Patents
Method for preparing ultrafine tungsten carbide powder by taking tungsten powder and glucose as raw materials Download PDFInfo
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- CN109231211B CN109231211B CN201811211136.1A CN201811211136A CN109231211B CN 109231211 B CN109231211 B CN 109231211B CN 201811211136 A CN201811211136 A CN 201811211136A CN 109231211 B CN109231211 B CN 109231211B
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- C01B32/00—Carbon; Compounds thereof
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Abstract
The invention provides a method for preparing superfine tungsten carbide powder by taking tungsten powder and glucose as raw materials, which comprises the following steps: the method comprises the following steps of mixing tungsten powder and glucose according to the mass ratio of 1: 1-1: 1.5, and preparing a mixed raw material; putting the mixed raw materials into a ball milling tank, adding grinding balls, and then performing inert gas protection or vacuum pumping treatment on the ball milling tank; placing the ball milling tank into a hearth of a ball mill, performing ball milling on the mixed raw materials through the ball mill, heating the hearth to 400-450 ℃ in the ball milling process, preserving heat for 30-40 min, then heating the hearth to 700-800 ℃, and preserving heat for 60-80 h; and closing the ball mill, cooling the hearth to room temperature, and taking out the ball milling tank to obtain the ultrafine tungsten carbide powder with uniform granularity. The method provided by the invention has the advantages of simple process, less energy consumption and low cost, can shorten the reaction time, and has high industrial value.
Description
Technical Field
The invention belongs to the technical field of preparation of superfine tungsten carbide powder, and particularly relates to a method for preparing superfine tungsten carbide powder by taking tungsten powder and glucose as raw materials.
Background
With the rapid development of science and technology, the demand of industrial production and daily life of people on hard alloy is increasing day by day. The superfine tungsten carbide (WC) is used as the most widely applied hard alloy material at present, has high hardness, good wear resistance, high strength and toughness, and is widely applied to the field of difficult-to-cut processing. In fact, all other conditions are equal, each property of the WC-based hard alloy, such as hardness, modulus, wear resistance, compressive strength and the like, is enhanced along with the reduction of the average grain size of WC, so that the preparation significance of the WC is profound. The metallic nickel is a common hard alloy binder, and the WC-Ni (Co) hard alloy has excellent wear resistance and corrosion resistance by adding a proper amount of proper additives. And the global reserve of nickel is huge, and the price basically cannot be influenced by the market to a great extent.
At present, the preparation process of the superfine WC with wider industrial application mainly comprises a tungsten oxide hydrogen reduction carbonization method and a high-energy ball milling method. The tungsten oxide hydrogen reduction carbonization method comprises the steps of introducing hydrogen into a high-temperature furnace to reduce tungsten trioxide into tungsten powder, mixing the tungsten powder and carbon black according to an equal molar ratio, and carbonizing at 1400-1600 ℃ in a hydrogen atmosphere; the high-energy ball milling method requires that tungsten powder and carbon powder are mixed uniformly and then put into a high-energy ball mill with the rotating speed as high as 800r/min for long-time ball milling, and the method has high requirement on the rotating speed of the ball mill, and the efficiency of the ball mill for crushing WC powder is low, so that a quite long crushing time is required, the particle size distribution of a product is difficult to control, and the powder performance is influenced.
In summary, there are some technical difficulties in the tungsten oxide hydrogen reduction carbonization method and the high energy ball milling method for producing the ultrafine tungsten carbide powder, and therefore, a process method suitable for producing the ultrafine tungsten carbide powder at a process level is required.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing ultrafine tungsten carbide powder by taking tungsten powder and glucose as raw materials.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a method for preparing superfine tungsten carbide powder by taking tungsten powder and glucose as raw materials comprises the following steps:
the method comprises the following steps of mixing tungsten powder and glucose according to the mass ratio of 1: 1-1: 1.5, and preparing a mixed raw material;
putting the mixed raw materials into a ball milling tank, adding grinding balls, and then performing inert gas protection or vacuum pumping treatment on the ball milling tank;
placing the ball milling tank into a hearth of a ball mill, performing ball milling on the mixed raw materials through the ball mill, heating the hearth to 400-450 ℃ in the ball milling process, preserving heat for 30-40 min, then heating the hearth to 700-800 ℃, and preserving heat for 60-80 h;
and closing the ball mill, cooling the hearth to room temperature, and taking out the ball milling tank to obtain the ultrafine tungsten carbide powder with uniform granularity.
Further, before the mixed raw materials are filled into the ball milling tank, a hard alloy binder accounting for 8-15% of the total mass of the tungsten powder and the glucose is added into the mixed raw materials.
Further, the hard alloy binder is one or a mixture of cobalt powder or nickel powder.
Further, when the mixed raw materials and the grinding balls are loaded into the ball milling tank, the mass ratio of the grinding balls to the mixed raw materials is 15-30: 1, wherein the grinding balls are stainless steel or tungsten carbide grinding balls with the diameter of 12 mm.
Further, when the mixed raw material is ball-milled by the ball mill, the rotation speed of the ball mill motor is 450 to 500 rpm.
Further, in the process of heating the hearth, the heating rate of the hearth is 4-6 ℃/min.
According to the method for preparing the ultrafine tungsten carbide powder by taking the tungsten powder and the glucose as the raw materials, the raw material formed by mixing the tungsten powder and the glucose is subjected to a mechanochemical method at a high temperature so as to complete one-step reaction between the tungsten powder and the glucose, so that the ultrafine tungsten carbide powder with uniform granularity can be obtained, the operation steps are reduced, the production time is saved, and a new method is provided for large-scale industrial production; in addition, the carbonization temperature of the conventional tungsten oxide hydrogen reduction carbonization method is greatly reduced from 1400-1600 ℃ to 700-800 ℃, and meanwhile, a high-speed ball mill is not needed, and the superfine WC powder with the average grain size of 0.225 mu m can be successfully prepared at a very low speed. Therefore, the preparation method of the ultrafine tungsten carbide powder provided by the invention has the advantages of simple process, low energy consumption and low cost, can shorten the reaction time, and has high industrial value.
Drawings
FIG. 1 is a schematic flow chart illustrating a method for preparing ultra-fine tungsten carbide powder from tungsten powder and glucose according to an exemplary embodiment of the present invention;
FIG. 2 is a schematic flow chart illustrating a method for preparing ultra-fine tungsten carbide powder from tungsten powder and glucose according to an exemplary embodiment of the present invention;
FIG. 3 is a diffraction pattern of XRD of the ultra fine tungsten carbide powder prepared in exemplary example 1 of the present invention;
FIG. 4 is a detection spectrum of a laser particle sizer of the ultra-fine tungsten carbide powder prepared in exemplary embodiment 1 of the present invention;
fig. 5 is a scanning electron microscope analysis picture of the ultra-fine tungsten carbide powder prepared in exemplary example 1 of the present invention.
Detailed Description
In order to overcome the defects in the prior art, the invention provides a method for preparing ultrafine tungsten carbide powder by taking tungsten powder and glucose as raw materials. In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be described in more detail below with reference to the accompanying drawings in the preferred embodiments of the present invention. The described embodiments are only some, but not all embodiments of the invention. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention. 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. Embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
As shown in fig. 1, a method for preparing ultra-fine tungsten carbide powder from tungsten powder and glucose as raw materials comprises:
s100, mixing tungsten powder and glucose according to a mass ratio of 1: 1-1: 1.5, and preparing a mixed raw material;
s200, filling the mixed raw materials into a ball milling tank of a ball mill, adding stainless steel or tungsten carbide grinding balls with the diameter of 12mm, wherein the mass ratio of the grinding balls to the mixed raw materials is 15-30: 1, and performing inert gas protection or vacuum pumping treatment on the ball milling tank;
s300, placing the ball milling tank into a hearth of a ball mill, and setting the rotating speed of the ball mill to be 450-500 rpm to perform ball milling on the mixed raw materials; in the ball milling process, heating the hearth to 400-450 ℃, preserving heat for 30-40 min, then heating the hearth to 700-800 ℃, and preserving heat for 60-80 h, wherein in the process of heating twice, the heating rate of the hearth is 4-6 ℃/min;
s400, closing the ball mill, cooling the hearth to room temperature, and taking out the ball milling tank to obtain the ultrafine tungsten carbide powder with uniform particle size.
According to the invention, tungsten powder and glucose are subjected to one-step reaction in a ball mill to obtain a final product, wherein the tungsten powder used in the invention is prepared without pretreatment of tungsten oxide, and the tungsten powder and the glucose powder are directly used as reactants; because the organic carbon source selected by the invention is glucose with high activity, the reaction can be promoted to be carried out, the glucose can be decomposed into carbon and water vapor at about 400 ℃ under the anaerobic condition, the carbon generated by decomposition has high activity and promotes the reaction to be accelerated, the glucose is adopted as the carbon source, the established effect can be generated, the reaction speed can be promoted to be superior to that of the conventional carbon powder, and meanwhile, the conventional carbonization temperature can be greatly reduced from 1400-1600 ℃ to 700-800 ℃ by the reaction of the mixed raw materials during heating and ball milling; in addition, the invention can successfully prepare the superfine WC powder with the average grain diameter of about 0.2 mu m at a very low rotating speed without using a high-rotating-speed ball mill. Therefore, the method has the advantages of simple process, low energy consumption, low cost, shortened reaction time and high industrial value.
In a preferred embodiment, before the mixed raw materials are loaded into the ball mill pot, a hard alloy binder is added to the mixed raw materials, wherein the hard alloy binder accounts for 8-15% of the total mass of the tungsten powder and the glucose.
Further, the hard alloy binder is one or a mixture of cobalt powder or nickel powder.
The mixed raw materials are reacted by a high-temperature mechanochemical method, and in the reaction process, under the condition that the reaction pressure is kept unchanged, the powder is further refined and dispersed more uniformly by the mechanical force of ball milling, the reactant and the product are continuously refined along with the reaction, the surface of the unreacted reactant is exposed timely by uninterrupted ball milling, so that carbon can enter the crystal lattice of tungsten more easily, the nickel powder and the cobalt powder are common hard alloy binders, the bonding effect is better after the nickel powder and the cobalt powder are mixed with the reactant according to a certain proportion, the reaction of the tungsten powder and the carbon powder is accelerated, and the bonding reaction of the carbon powder and the tungsten powder is promoted more. In addition, the proper ball milling refines crystal grains and increases the specific surface area, thereby improving the kinetic condition, leading the reaction to be more complete at high temperature and also being realized at lower temperature, and reducing the occurrence of agglomeration phenomenon due to the existence of the ball milling.
The method for preparing ultra-fine tungsten carbide powder using tungsten powder and glucose as raw materials according to the present invention is specifically described below by way of examples.
Example 1
As shown in fig. 2, a method for preparing ultra-fine tungsten carbide powder from tungsten powder and glucose as raw materials comprises:
s100, uniformly mixing 90g of tungsten powder and 100g of glucose powder, and adding 19g of cobalt powder to prepare a mixed raw material;
s200, filling the mixed raw materials into a ball milling tank of a ball mill, adding stainless steel or tungsten carbide grinding balls with the diameter of 12mm, wherein the mass ratio of the grinding balls to the mixed raw materials is 15:1, and performing inert gas protection or vacuum pumping treatment on the ball milling tank;
s300, placing the ball milling tank into a hearth of a ball mill, and setting the rotating speed of the ball mill to be 450-500 rpm to perform ball milling on the mixed raw materials; in the ball milling process, heating the hearth to 400 ℃, preserving heat for 30min, then heating the hearth to 800 ℃, and preserving heat for 60h, wherein in the process of heating twice, the heating rate of the hearth is 4 ℃/min;
s400, closing the ball mill, cooling the hearth to room temperature, and taking out the ball milling tank to obtain the ultrafine tungsten carbide powder with uniform particle size.
Example 2
S100, uniformly mixing 60g of tungsten powder and 60g of glucose powder, and adding 15g of nickel powder to prepare a mixed raw material;
s200, filling the mixed raw materials into a ball milling tank of a ball mill, adding stainless steel or tungsten carbide grinding balls with the diameter of 12mm, wherein the mass ratio of the grinding balls to the mixed raw materials is 20:1, and performing inert gas protection or vacuum pumping treatment on the ball milling tank;
s300, placing the ball milling tank into a hearth of a ball mill, and setting the rotating speed of the ball mill to be 450-500 rpm to perform ball milling on the mixed raw materials; in the ball milling process, heating the hearth to 430 ℃, preserving heat for 35min, then heating the hearth to 750 ℃, and preserving heat for 70h, wherein in the process of heating for two times, the heating rate of the hearth is 5 ℃/min;
s400, closing the ball mill, cooling the hearth to room temperature, and taking out the ball milling tank to obtain the ultrafine tungsten carbide powder with uniform particle size.
Example 3
S100, uniformly mixing 70g of tungsten powder and 105g of glucose powder, and adding 13g of cobalt powder and 13g of nickel powder to prepare a mixed raw material;
s200, filling the mixed raw materials into a ball milling tank of a ball mill, adding stainless steel or tungsten carbide grinding balls with the diameter of 12mm, wherein the mass ratio of the grinding balls to the mixed raw materials is 30:1, and performing inert gas protection or vacuum pumping treatment on the ball milling tank;
s300, placing the ball milling tank into a hearth of a ball mill, and setting the rotating speed of the ball mill to be 450-500 rpm to perform ball milling on the mixed raw materials; in the ball milling process, heating the hearth to 450 ℃, preserving heat for 40min, then heating the hearth to 800 ℃, and preserving heat for 80h, wherein in the process of heating for two times, the heating rate of the hearth is 6 ℃/min;
s400, closing the ball mill, cooling the hearth to room temperature, and taking out the ball milling tank to obtain the ultrafine tungsten carbide powder with uniform particle size.
When the ultrafine tungsten carbide powder prepared in example 1 is subjected to XRD detection, laser granulometer detection, and scanning electron microscope analysis, the following conclusions can be drawn:
as shown in fig. 3, the XRD pattern shows sharp peaks of tungsten carbide, which correspond one-to-one to standard peaks of tungsten carbide, and no excessive impurity peaks, thus indicating that the crystallinity of the tungsten carbide powder is good.
As shown in fig. 4, the volume of the product powder with a particle size of 0.2 μm is at most, approximately 20%, which can be analyzed by a spectrum of the particle size detected by a laser particle sizer, and it can be said that the particle size of the tungsten carbide powder is small.
As shown in fig. 5, the tungsten carbide powder was observed to be uniform, free from agglomeration and granular by analyzing the pictures of the scanning electron micrograph thereof.
Finally, it should be noted that the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to examples, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (5)
1. A method for preparing superfine tungsten carbide powder by taking tungsten powder and glucose as raw materials is characterized by comprising the following steps:
the method comprises the following steps of mixing tungsten powder and glucose according to the mass ratio of 1: 1-1: 1.5, and preparing a mixed raw material;
putting the mixed raw materials into a ball milling tank, adding grinding balls, and then performing inert gas protection or vacuum pumping treatment on the ball milling tank;
placing the ball milling tank into a hearth of a ball mill, performing ball milling on the mixed raw materials through the ball mill, heating the hearth to 400-450 ℃ in the ball milling process, preserving heat for 30-40 min, then heating the hearth to 700-800 ℃, and preserving heat for 60-80 h;
closing the ball mill, cooling the hearth to room temperature, and taking out the ball milling tank to obtain ultrafine tungsten carbide powder with uniform particle size;
wherein, when the mixed raw material is ball-milled by the ball mill, the rotation speed of the motor of the ball mill is 450-500 rpm.
2. The method for preparing ultrafine tungsten carbide powder from tungsten powder and glucose as raw materials according to claim 1, wherein a cemented carbide binder is added to the mixed raw materials in an amount of 8-15% by mass of the total mass of tungsten powder and glucose before the mixed raw materials are charged into the ball mill pot.
3. The method for preparing ultrafine tungsten carbide powder from tungsten powder and glucose as raw materials according to claim 2, wherein the hard alloy binder is one or a mixture of cobalt powder and nickel powder.
4. The method for preparing ultrafine tungsten carbide powder from tungsten powder and glucose as raw materials according to claim 1, wherein the mass ratio of the grinding balls to the mixed raw materials is 15-30: 1 when the mixed raw materials and the grinding balls are loaded into the ball mill pot, wherein the grinding balls are stainless steel or tungsten carbide grinding balls with a diameter of 12 mm.
5. The method for preparing ultra-fine tungsten carbide powder from tungsten powder and glucose as raw materials according to any one of claims 1 to 4, wherein the temperature rise rate of the hearth is 4-6 ℃/min during the temperature rise of the hearth.
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Patent Citations (7)
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| US6793875B1 (en) * | 1997-09-24 | 2004-09-21 | The University Of Connecticut | Nanostructured carbide cermet powders by high energy ball milling |
| CN1424252A (en) * | 2003-01-03 | 2003-06-18 | 浙江大学 | Preparation of tungsten carbide powder |
| CN101003024A (en) * | 2006-09-19 | 2007-07-25 | 东北大学 | High temperature energy ball grinder |
| CN101798083A (en) * | 2010-03-05 | 2010-08-11 | 中国兵器工业第五二研究所 | Method for preparing tungsten carbide powder through self-propagating process |
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