CN109722069B - Environment-friendly high-adhesion hard alloy anti-sticking coating and preparation method and application thereof - Google Patents
Environment-friendly high-adhesion hard alloy anti-sticking coating and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to an environment-friendly high-adhesion hard alloy anti-sticking coating, a preparation method and application thereof, wherein the coating comprises the following components in percentage by mass: 10-20% of high-purity carbon black, 25-60% of alumina, 3-10% of superfine aluminum hydroxide, 5-10% of phenolic aldehyde polyglycidyl ether and the balance of deionized water; during preparation, firstly, weighing high-purity carbon black, alumina powder, superfine aluminum hydroxide and phenolic aldehyde polyglycidyl ether according to the mass percentage, and the balance being deionized water; then placing the materials into a ball milling tank for ball milling, wherein the ball-material ratio is 2-5: 1, carrying out wet milling for 25-50 hours, and controlling the ball milling rotation speed to be 25-40 r/min; and after the ball milling is finished, the mixture is screened to obtain a coating, and the coating is stored in a sealed container and is stored in a shade place. The method is suitable for sintering the hard alloy with the cobalt content of 5-25 wt%, and the hard alloy can be used for 3-5 times by brushing the material tray once.
Description
Technical Field
The invention relates to an environment-friendly high-adhesion hard alloy anti-sticking coating and a preparation method and application thereof.
Background
At present, the hard alloy generally refers to an alloy material made of WC powder and Co powder through a powder metallurgy process, and the basic production process of the hard alloy comprises forming and sintering. The sintering of hard alloy belongs to typical liquid phase sintering, the sintering temperature is usually above 1380 ℃, a graphite boat is usually adopted as a bearing container for sintering the hard alloy, and a product after compression molding is loaded into the graphite boat and then is sent into a sintering furnace for sintering. The graphite boat has the characteristics of high strength at high temperature, capability of preventing hard alloy products from decarbonizing during high-temperature sintering, relatively low price and the like, but because the wetting angle between metal cobalt and graphite is very small, a bonding phase formed during liquid phase sintering can diffuse and migrate towards the graphite boat, so that the products are carburized and even bonded with the graphite boat, and the products and the graphite boat are scrapped.
The existing hard alloy sintering anti-sticking method mainly comprises four methods: spreading anti-sticking paper for isolation, spreading corundum sand for isolation, plasma spraying coating disc for isolation and brushing anti-sticking coating for isolation. The former two methods can cause pollution to a sintering furnace hearth and even block a gas pipeline, and the plasma spraying coating plate is formed by spraying a layer of ceramic coating (comprising zirconium oxide, aluminum oxide, yttrium oxide and the like) on the surface of a graphite boat so as to play a role in isolation, but the plasma spraying coating cost is higher, the thermal expansion coefficient of the graphite and the coating is different, the service life of the spraying coating plate is not long in a repeated cold and hot alternate use environment and is generally not more than 20 times, so that the total cost is higher. Therefore, the method of anti-sticking coating isolation is still widely used in various carbide alloy factories at present.
The anti-sticking coating which is widely used at present comprises carbon black, metal oxide, an organic dispersant, a surfactant, a defoaming agent, a solvent and the like, can be used for sintering various hard alloys, but has various components and contains organic matters such as polyethylene glycol, tween, n-butyl alcohol, urotropine and the like, and can affect the production environment. The organic matters can volatilize and decompose in the high-temperature sintering process, have no direct effect on adhesion prevention, and damage the coating structure coated on the surface of the graphite boat before sintering due to the volatilization and decomposition of the organic matters, so that the coating forms a loose and porous network structure, and the bonding phase infiltration coating layer in the liquid phase sintering process is increased to cause carburization and even boat adhesion. After sintering is completed, the surface coating of the graphite boat is loose and is easy to be adsorbed or adhered to the surface of an alloy product, so that the environment of a sintering furnace unloading area is dirty and bad, the graphite boat needs to be cleaned and recoated after sintering is completed every time, and the labor intensity of operators is high.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides an environment-friendly high-adhesion hard alloy anti-sticking coating as well as a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme:
the environment-friendly high-adhesion hard alloy anti-sticking coating is characterized in that: the weight percentage of the components is as follows:
further, the purity of the high-purity carbon black is more than or equal to 99.9%.
Further, in the environment-friendly high-adhesion hard alloy anti-sticking coating, the alumina is 200-300 meshes of alumina.
Further, the environment-friendly high-adhesion hard alloy anti-sticking coating has the particle size of 0.5-2 μm.
The preparation method of the environment-friendly high-adhesion hard alloy anti-sticking coating comprises the following steps:
1) weighing high-purity carbon black, alumina powder, superfine aluminum hydroxide and phenolic aldehyde polyglycidyl ether according to the mass percentage, and the balance being deionized water;
2) placing the materials into a ball milling tank for ball milling, wherein the ball material ratio is 2-5: 1, carrying out wet milling for 25-50 hours, and controlling the ball milling rotation speed to be 25-40 r/min;
3) and after the ball milling is finished, the mixture is screened to obtain a coating, and the coating is stored in a sealed container and is stored in a shade place.
Furthermore, in the preparation method of the environment-friendly high-adhesion hard alloy anti-sticking coating, wet grinding balls in the ball-milling tank are hard alloy balls, and the ball diameter is 6-10 mm.
Furthermore, in the preparation method of the environment-friendly high-adhesion cemented carbide anti-sticking coating, the mixture is screened by a 100-mesh screen after the ball milling is finished to obtain the coating.
The environment-friendly high-adhesion hard alloy anti-sticking coating is applied to the surface of a cleaned graphite boat after being stirred for 5-10 minutes before being used, and can be used after being dried for 4 hours in a drying oven at 250 ℃.
Compared with the prior art, the invention has obvious advantages and beneficial effects, and is embodied in the following aspects:
the environment-friendly high-adhesion cemented carbide anti-sticking coating can be suitable for sintering cemented carbide with 5-25 wt% of cobalt, and a material plate can be used for 3-5 times by once coating, so that the production cost is reduced, the labor intensity of boat coating operators is reduced, and the working environment of sintering operators is improved.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by the practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims thereof.
Detailed Description
In order to more clearly understand the technical features, objects, and effects of the present invention, specific embodiments will now be described in detail.
The environment-friendly high-adhesion hard alloy anti-sticking coating comprises the following components in percentage by mass: 10-20% of high-purity carbon black, 25-60% of alumina, 3-10% of superfine aluminum hydroxide, 5-10% of phenolic aldehyde polyglycidyl ether and the balance of deionized water. Wherein the purity of the high-purity carbon black is more than or equal to 99.9 percent, the alumina is 200-300 meshes of alumina, and the granularity of the superfine aluminum hydroxide is 0.5-2 mu m.
The specific preparation process comprises the following steps:
1) weighing high-purity carbon black, alumina powder, superfine aluminum hydroxide and phenolic aldehyde polyglycidyl ether according to the mass percentage, and the balance being deionized water;
2) placing the materials into a ball milling tank for ball milling, wherein wet milling balls in the ball milling tank are hard alloy balls, the ball diameter is 6-10 mm, the ball-material ratio is 2-5: 1, wet milling is carried out for 25-50 hours, and the ball milling rotating speed is controlled to be 25-40 r/min;
3) and (4) after the ball milling is finished, the mixture passes through a 100-mesh screen to obtain a coating, and the coating is stored in a sealed container and stored in a shade place.
Stirring for 5-10 minutes before use, brushing the mixture on the surface of a cleaned graphite boat, and drying the graphite boat for 4 hours in a drying oven at 250 ℃.
Example 1
According to the mass percentage of the components: 18% of high-purity carbon black, 35% of aluminum oxide, 5% of aluminum hydroxide, 6% of phenolic aldehyde polyglycidyl ether and 36% of deionized water.
The components are proportionally filled into a ball milling tank, a ball milling barrel is opened, the ball milling ratio in the ball milling barrel is 3:1, the ball milling rotating speed is 35 r/min, discharging is carried out after ball milling is carried out for 30 hours, and a uniform turbid liquid is obtained by passing through a 100-mesh screen. The coating is uniformly coated on a cleaned graphite boat, dried for 4 hours at 250 ℃ in a drying oven, and cooled to be put into use.
The hard alloy bar and plate with the cobalt content less than 15 wt% is sintered by the tray coated and dried by the environment-friendly high-adhesion hard alloy anti-sticking coating, and the problems of carburization and boat sticking are avoided. The bending rate of the bar obtained by the first sintering is 1 percent, and the flatness of the plate is within 0.2 mm. After the material tray is repeatedly used for 4 times, the bending rate of the bar stock is only 5%, and the flatness of the plate is within 0.45 mm.
It should be noted that the alloy cannot be dragged when it is removed from the tray after sintering is completed, which would result in the coating layer falling off locally and not being reused.
Example 2
According to the mass percentage of the components: 13% of high-purity carbon black, 48% of aluminum oxide, 7% of aluminum hydroxide, 10% of phenolic aldehyde polyglycidyl ether and 22% of deionized water.
The components are proportionally filled into a ball milling tank, a ball milling barrel is opened, the ball milling ratio in the ball milling barrel is 3:1, the ball milling rotating speed is 35 r/min, discharging is carried out after ball milling is carried out for 30 hours, and a uniform turbid liquid is obtained by passing through a 100-mesh screen. The coating is uniformly coated on a cleaned graphite boat, dried for 4 hours at 250 ℃ in a drying oven, and cooled to be put into use.
Example 3
According to the mass percentage of the components: 10% of high-purity carbon black, 55% of alumina, 7% of aluminum hydroxide, 10% of phenolic aldehyde polyglycidyl ether and 18% of deionized water.
The components are proportionally filled into a ball milling tank, a ball milling barrel is opened, the ball milling ratio in the ball milling barrel is 3:1, the ball milling rotating speed is 35 r/min, discharging is carried out after ball milling is carried out for 30 hours, and a uniform turbid liquid is obtained by passing through a 100-mesh screen. The coating is uniformly coated on a cleaned graphite boat, dried for 4 hours at 250 ℃ in a drying oven, and cooled to be put into use.
The carbon black plays a role in dispersing alumina and aluminum hydroxide particles, can balance carbon atmosphere in the furnace during sintering, and the phenolic aldehyde polyglycidyl ether serves as a film forming agent and plays a role in strengthening a coating layer after the charging tray is coated and dried.
Alumina is used as the main component of the coating and is coated on the surface of the tray to form an isolating layer.
Adding aluminum hydroxide into the coating, mixing and ball-milling the mixture, and uniformly distributing the mixture around the aluminum oxide and carbon black particles. And when the coated material disc is dried at 250 ℃, aluminum hydroxide is dehydrated to generate aluminum oxide, and primary aluminum oxide particles are used as crystal nuclei to grow to form an isolating layer together with the primary aluminum oxide particles.
Most of the crystal water decomposed from deionized water and aluminium hydroxide is directly discharged, and a small part of the crystal water reacts with carbon black with higher activity in the coating under the catalytic action of aluminium oxide to produce CO and CO2Is eliminated, thereby reducing the influence of the coating on the carbon atmosphere in the sintering furnace in the high-temperature sintering process. And because the aluminum oxide is used as a crystal nucleus, the phase change activation energy of the aluminum hydroxide is reduced, so that the phase and structure transition temperature of the aluminum hydroxide is reduced. Along with the rise of sintering temperature, the hard alloy does not have a liquid phase at about 1000 ℃, aluminum hydroxide finishes the transformation of phase and structure, an aluminum oxide isolation layer which takes initial aluminum oxide particles as a framework and subsequently grown aluminum oxide as filling is formed, the aluminum oxide particles are chelated with each other, and certain compactness and strength are achieved, so that the carburization and boat adhesion tendency of the hard alloy in the liquid phase sintering process is prevented. The surface coating layer of the graphite boat after one-time sintering has higher strength, is not easy to fall off, can be used for multiple times, can be generally used for 3-5 times, and then is removed and coated again, so that the production cost is further reduced.
In conclusion, the environment-friendly high-adhesion-force hard alloy anti-sticking coating disclosed by the invention is suitable for sintering hard alloy with the cobalt content of 5-25 wt%, and can be used for 3-5 times by brushing a tray once, so that the production cost is reduced, the labor intensity of a boat brushing operator is reduced, and the working environment of the sintering operator is improved.
It should be noted that: the above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention; while the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (4)
1. The preparation method of the environment-friendly high-adhesion cemented carbide anti-sticking coating is characterized by comprising the following steps:
the environment-friendly high-adhesion hard alloy anti-sticking coating comprises the following components in percentage by mass:
the preparation process comprises the following steps:
1) weighing high-purity carbon black, alumina powder, superfine aluminum hydroxide and phenolic aldehyde polyglycidyl ether according to the mass percentage, and the balance being deionized water;
2) placing the materials into a ball milling tank for ball milling, wherein the ball material ratio is 2-5: 1, carrying out wet milling for 25-50 hours, and controlling the ball milling rotation speed to be 25-40 r/min;
3) after the ball milling is finished, the mixture is screened to obtain a coating, the coating is stored in a sealed container and is stored in a shade place;
the environment-friendly high-adhesion cemented carbide anti-sticking coating is applied to cemented carbide sintering with 5-25 wt% of cobalt content.
2. The preparation method of the environment-friendly high-adhesion cemented carbide anti-sticking coating as claimed in claim 1, characterized in that: the wet grinding balls in the ball milling tank are hard alloy balls, and the ball diameter is phi 6-phi 10 mm.
3. The preparation method of the environment-friendly high-adhesion cemented carbide anti-sticking coating as claimed in claim 1, characterized in that: and (4) after the ball milling is finished, the mixture passes through a 100-mesh screen to obtain the coating.
4. The application of the coating obtained by the preparation method of the environment-friendly high-adhesion cemented carbide anti-sticking coating according to claim 1 is characterized in that: stirring for 5-10 minutes before use, brushing the mixture on the surface of a cleaned graphite boat, and drying the graphite boat for 4 hours in a drying oven at 250 ℃.
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| CN102277019A (en) * | 2011-07-20 | 2011-12-14 | 中南大学 | High-temperature anti-adhesive coating for producing hard alloy and preparation method thereof |
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