WO2001078924A1

WO2001078924A1 - PROCESS AND GRINDING APPARATUS FOR PREPARING NANOMETER SCALE Ti-BASE METAL POWDER

Info

Publication number: WO2001078924A1
Application number: PCT/CN2001/000558
Authority: WO
Inventors: Junfeng Xue; Fujin Xue
Original assignee: Junfeng Xue; Fujin Xue
Priority date: 2000-04-17
Filing date: 2001-04-17
Publication date: 2001-10-25
Also published as: CN1124911C; AU2001273787A1; CN1266760A

Abstract

A process for preparing nanometer scale Ti-base metal powder is provided, in which titanium powder, pulverizing aid, protective agent and disperser are mixed together in the right proportion and grinded by a grinding apparatus to perform mechanochemical reaction so as to obtaining nanometer scale Ti-base metal powder. A grinding apparatus for preparing nanometer scale Ti-base metal powder is also disclosed. The invention provides possibilities for preparing polymer paint of nanometer scale Ti-base metal powder used as filler, and provides a new filler for producing titanium repairing agent. Being an active filler and a coupling agent, the filler is especially effective in anticorrosion and antiwear performance of paint.

Description

Method for manufacturing titanium-based nano metal powder and grinding device

The invention relates to a method for manufacturing titanium-based nano metal powder, which belongs to the field of metal material processing. The invention also relates to a titanium-based nano metal powder grinding device used in the manufacturing method.

Background technique

With the advancement of science and technology, people's requirements for high-performance materials are more and more urgent, and new high-performance materials synthesized with nanoparticles provide a new way to improve the performance of existing materials. Disperse nanoparticles into conventional three-dimensional solids, such as dispersing metal nanoparticles into a metal or alloy or adding conventional ceramic materials or polymers. The nanocomposite material obtained by this method is the scientific research of nanocomposite materials today. One of the hot spots. Among them, polymer-based nano-polymer materials (or nano-polymer materials) are one of the most promising composite materials.

With the advent of nanomaterials, modification of coatings with nanoscale fillers is a frontier subject of science and technology.

As an industrial corrosion-resistant basic material, titanium metal is second only to tantalum and niobium, but its price is much lower. Therefore, corrosion resistance materials made of titanium have great economic value.

Therefore, an object of the present invention is to provide a method for manufacturing titanium-based nano-metal powder, by which a titanium-based nano-metal powder filler necessary for significantly improving polymer performance is prepared by this simpler method, thereby realizing polymer material modified.

Another object of the present invention is to provide a titanium-based nano metal powder.

It is still another object of the present invention to provide a grinding apparatus which can be used to implement the above method to prepare titanium-based nano metal powder.

The titanium-based nano-metal powder prepared by the method for manufacturing titanium-based nano-metal powder according to the present invention provides the possibility for the preparation of polymer coatings using titanium-based nano-metal powder as a filler, and provides a method for the production of titanium repairing agents A new type of concrete, which is both an active filler and a coupling agent, has a special role in providing coatings with corrosion resistance and wear resistance.

Summary of invention

The invention provides a method for preparing titanium-based nano metal powder, which method includes the following two stages: (1) Pre-treatment stage: 100 parts by weight of metal titanium powder is mixed with 0.5-30 parts by weight of a grinding aid, 0.1-20 parts by weight of a protective agent, and 100-1000 parts by weight of a dispersant to perform pretreatment;

(2) Grinding stage: The metal titanium powder equipped with the above dispersant, protective agent and dispersant is put into a grinding device, and after grinding, titanium-based nano powder with a fineness of 10-100 nm is produced.

The invention also provides a titanium-based nano-metal powder, which is in a coating form, and the titanium content of the metal powder is more than 90% by weight, preferably 93-95% by weight.

The present invention also provides a grinding device for implementing the above preparation method. The grinding device includes a main shaft 1, which is arranged substantially parallel to each other, at least two auxiliary shafts 2, at least two rotating cylinders 3 which are symmetrically arranged with respect to the main shaft, and is used for connecting the main shaft. A connection device with a countershaft, one end of the connection device is installed on the main shaft and can rotate with the main shaft. Each drum 3 is supported on and rotates with a respective countershaft, and the countershaft is rotatable about its own axis. The grinding device is supported at the other end of the connecting device and can rotate with the connecting device about the main shaft. The grinding device further includes a driving device for realizing the rotation of the rotating drum around the auxiliary shaft and the orbiting of the main shaft. Grinding body.

The transmission of the grinding device is realized as follows: the main shaft 1 is driven by a motor through a transmission wheel, and the countershaft 2 is driven by the main shaft 1 through a speed change device 8 or directly driven by an independent power system. There are at least two rotating drums 3 Rotate around the secondary shaft 2, where the rotation speed of the primary shaft 1 is set to 100-1000 rpm, and the rotation speed ratio of the primary shaft 1 to the secondary shaft 2 is set to 1: 2 to 10, and the aspect ratio of the drum 3 is at least 10:

1

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic plan view of a titanium-based nano metal powder grinding device according to the present invention.

Fig. 2 is a schematic cross-sectional view of a preferred embodiment of the titanium-based nano metal powder grinding device according to the present invention.

Detailed description of the invention

The invention provides a method for preparing titanium-based nano metal powder, which method includes the following two stages:

(1) Pre-treatment stage: 100 parts by weight of metal titanium powder is mixed with 0.5-30 parts by weight of a grinding aid, 0.1-20 parts by weight of a protective agent, and 100-1000 parts by weight of a dispersant to perform pretreatment;

(2) Grinding stage: The metal titanium powder provided with the co-dispersant, the protective agent and the dispersant is charged into a grinding device, and after grinding, titanium-based nano powder having a fineness of 10-100 nm is produced. In the above method for preparing titanium-based nano metal powder, the pulverizing aid is an oligomer or polymer having unsaturated functional groups, including polyvinyl acetate, polyacrylate, low molecular weight polyamide, oleic acid, and polysilicon. One or more of oxane;

The protective agent is one or more of a low molecular weight phenol and its prepolymer, an epoxy compound, a sulfur-containing rubber, a chlorinated rubber, polyvinyl alcohol, polyaluminum ethylsiloxane, or polysiloxane;

The dispersant is one or more of aromatic compounds, styrene, hydrocarbons, chlorohydrocarbons, alcohols, ketones or acetates.

In the pre-treatment stage, multi-step pre-treatment can also be adopted according to the co-dispersant, protective agent and dispersant used. For example, all or part of the auxiliary pulverizer, protective agent and dispersant are mixed and reacted for a period of time, and then titanium powder and the remaining components (if any) are added for pretreatment.

In a preferred embodiment of the method for preparing a titanium-based nano metal powder, the reaction time in the pretreatment stage is 0.5 hours, preferably 1 hour or more, and the reaction temperature is preferably 50-100 ° C; the reaction temperature in the grinding stage is preferably 70. -150 ° C, grinding time is 1-5 hours.

In a preferred embodiment of the present invention, the dispersant is ( _2- ( ₈ alcohols, C ₃ -C ₆ ketones).

The invention also provides a titanium-based nano metal powder prepared according to the method, the metal powder is in a coating form, and the titanium content in the metal powder is more than 90% by weight, and preferably 93-95% by weight.

The invention also provides a coated titanium-based nano metal powder. The starting material of the metal powder is: 100 parts by weight of metal titanium powder, 0.5-30 parts by weight of a grinding aid, and 0.1-20 parts by weight of protection. Agent and 100 to 1000 parts by weight of a dispersant; the pulverizer, the protective agent and the dispersant are as defined above.

The invention also relates to a grinding device with a high-efficiency pulverizing function, in particular to a high-energy grinding device capable of achieving ultra-fine refinement of hard substances, surface modification, preparation of metal polymers, and production of nano-materials, in particular to production of titanium-based nano Grinding device for metal powder.

The structure of the grinding apparatus of the present invention will be described in detail with reference to the accompanying drawings.

As shown in FIG. 1, the grinding device of the present invention includes a main shaft 1 and an auxiliary shaft 2 arranged substantially in parallel with each other. The main shaft 1 is driven to rotate by a motor 9. The countershaft 2 can be driven by the main shaft 1 via a transmission device or directly by an independent power system. Preferably, the grinding device has at least two rotating drums 3, and each rotating drum 3 is mounted on a respective secondary shaft 2 and rotates with it. The rotation speed of the main shaft 1 is set to 100-1000 rpm, and the rotation speed ratio of the main shaft 1 and the auxiliary shaft 2 is set to 1: 2 to 10, and the length / diameter of the rotating barrel 3 The ratio (abbreviated as aspect ratio) is preferably at least 10: 1.

The drum 3 also contains a plurality of abrasive bodies. The diameter of the grinding body is 5 mm to 30 mm, the mass of the grinding body is 10 to 10 grams, and the mass ratio of the grinding body to the material is between 1: 1 to 10: 1. According to different crushing objects, the grinding body can be made of different materials, including but not limited to, such as bearing steel, special tungsten alloy, fused zirconia, agate, nickel-based wear-resistant alloy, etc.

The device of the present invention integrates the crushing, grinding, free-impact crushing, hindered impact crushing, chopping, crushing, shearing and other methods used in crushing materials, and in a short time, the materials From macroscopic particle crushing to less than 1 micron to less than 100 nanometers, no classification treatment is required, which provides the possibility for large-scale production of nanomaterials.

Two or more parallel rotating bodies 4 are installed on the main shaft 1, and the parallel rotating bodies 4 can rotate together with the main shaft 1. A hole is formed at the radially outer end of the parallel rotating body 4, and the counter shaft 2 is supported in the hole through a bearing, so that the secondary shaft 2 can rotate about its own axis relative to the parallel rotating body 4. As shown in the figure, the grinding device is provided with two parallel rotating bodies 4, which are respectively installed on both sides of the rotating drum 3. When the grinding device is running, the main shaft 1 is rotated by the motor. On the one hand, the main shaft 1 drives the auxiliary shaft 2 to rotate through the transmission 8 so that the auxiliary shaft 2 drives the drum 3 to rotate around its own axis; on the other hand, the main shaft 1 rotates in parallel. It can be seen that while the drum 3 rotates around the axis of the secondary shaft 2, it revolves around the axis of the main shaft 1.

As shown in the preferred embodiment shown in FIG. 2, the main shaft 1 is rotated by a motor through a transmission wheel, and the speed change device 8 between the main shaft and the countershaft is driven by a driving gear 5 mounted on the main shaft 1 and a slave gear mounted on the countershaft 2. The moving gear 6 is constituted, and the rotation of the main shaft 1 is transmitted to the counter shaft 2 via the above-mentioned transmission device 8.

In the grinding device, the rotation speed of the main shaft is 100-1000 rpm, and the speed ratio of the main shaft 1 and the auxiliary shaft 2 is between 1: (2-10).

The two ends of the rotating drum 3 are connected to the corresponding auxiliary shaft 2 by means of flanges on the ends, or the rotating drum 3 itself functions as the auxiliary shaft 2.

The length-to-diameter ratio of the drum 3 is at least 10: 1, preferably 10: 1 ~ 30: 1. For example, when the diameter is 35mm, the length of the drum 3 can reach 500mm; and when the diameter is 89mm, the length It can reach 2000mm, which can ensure that the titanium powder is always in a thin layer in the state of being impacted, squeezed and ground in the drum, thereby greatly improving the grinding effect.

In order to realize the rotation of the rotating drum 3 about the axis of the lay shaft 2, different driving modes may be adopted. The countershaft 2 can be rotated by the main shaft through a transmission device, or it can be driven by an independent power system. Turn. In the case of using an independent driving system, the rotation of the independent power system of each drum 3 should be synchronized, same direction, and same speed.

According to the actual application requirements, the titanium-based nano-metal powder grinding device of the present invention may also be equipped with a finned radiator on the material drum 3, or a cooling device may be provided on the entire device to control the temperature of the device and extend the equipment. Life and material temperature. For example, the temperature of the material in the drum 3 can be controlled by one of the following methods or a combination thereof:

-Adding cooling materials while adding materials;

-Cool down the material to a lower specified temperature in advance;

-A protective and cooling environment is established around the entire device. During the production process, by the rotation of the drum 3, the material heat is transmitted by the fins.

For example, the ambient temperature of the device can be controlled in such a way that the entire device is placed in a semi-enclosed environment. According to the requirements of the ambient temperature, the protective temperature-reducing gas that has been cooled and dehumidified is intermittently introduced to adjust the ambient temperature.

In addition, in the titanium-based nano-metal powder grinding device of the present invention, the loading and unloading of materials in the rotating drum 3 is automatically inclined by the whole machine to form an angle of (30 ~ 45 degrees) to (120-135 degrees) with the axis of the rotating drum 3 After that, it is automatically released or loaded. Examples

The present invention will be further described below with reference to specific embodiments of the present invention. It should be understood that these specific contents are not intended to limit the protection scope of the present invention. The starting materials used in the examples are known, prepared by known methods, or commercially available as starting materials. The raw titanium powder used in the examples is commercially available, wherein the titanium content is preferably 97% by weight or more, and the particle diameter of the titanium powder is preferably 80-120 mesh. The specific surface area is measured by a low-temperature argon adsorption method, and the average particle size of the powder is measured by a transmission electron microscope.

Example 1

A solution of phenol and formaldehyde in a molar ratio of 1: 1.1 to 1.6 was prepared, and the mixture was refluxed under alkali catalysis for 20 to 30 minutes, followed by dehydration treatment to obtain a protective agent of a certain viscosity, a phenolic prepolymer.

Take 200 parts by weight of the above phenolic acid prepolymer, add 800 parts by weight of dispersant-ethanol, and 80 parts by weight of pulverizer-oleic acid, react at 50-60 ° C for 1.5 hours, and filter to obtain a light brown viscous liquid.

Take 100 parts by weight of titanium powder, add 70 parts by weight of the above-mentioned filtrate, 630 parts by weight of dispersant-ethanol, and leave it at room temperature for 24 hours, and then grind it with a titanium-based nano-metal powder grinding device for 3.5 hours to obtain The titanium-based nano metal powder has a specific surface of 8.8 m ² / g. Example 2

Put 22.5mol of bisphenol A, 225mol of epichlorohydrin, and 104g of water into the reactor, gradually add 1880g of NaOH under cooling and stirring, and maintain the solution condensation at 90-100 ° C. After completion, add benzene to desalinate to recover low The molecular weight epoxy compound has a molecular weight of 100-170.

Take 100 parts by weight of the above epoxy compound (protective agent), add 500 parts by weight of dispersant-toluene, and 10 parts by weight of pulverizer-polymethyl acrylate (commercially available) to react at 50 ± 5 ° C for 1.5 hours. Add 200 parts by weight of dispersant-xylene and filter for later use.

Take 100 parts by weight of the above-mentioned filtrate, add 100 parts by weight of titanium powder, and immerse for 24 hours, then add 800 parts by weight of dispersant-toluene and mix, and grind and react on a titanium-based nano-metal grinding device for 4.5 hours to obtain titanium-based nano-metal powder. The specific surface area was 10.5 m ² / g. Example 3

100 parts by weight of titanium powder and a pulverizing agent-7 parts by weight of a primary polymer of methyl methacrylate (commercially available), a pulverizing agent and a protecting agent-20 parts by weight of a polysiloxane polycondensate having a molecular weight of 800-1200 Mix and pre-treat at 70-80 ° C for 1-2 hours. After cooling, add dispersant-900 parts by weight of pentanone and mix thoroughly to obtain a pre-treatment product. After the precipitate is left for 24 hours, the upper clear solution (mainly 戍Ketone) after taking out 300 parts by weight, and then adding dispersant-100 parts by weight of xylene, butanol, and 10 parts by weight of hexane each, and then performing ultra-fine grinding reaction on a titanium-based nano metal powder grinding device for 1 hour, and then taking out After being placed at constant weight at room temperature, a titanium-based nano metal powder was obtained, and its specific surface area was 5.8 m ² / g. Example 4

100 parts by weight of titanium powder is first impregnated with dispersant-400 parts by weight of ethyl acetate for 8-10 hours, and then a protective agent-sulfur-containing rubber having a molecular weight of 1200-1600 is added 8 parts by weight, and pre-reacted at 50-60 ° C 3 Hours, and then add 5 parts by weight of polyvinyl acetate, a constant temperature of 50-55 ° C for 10-15 hours, and then cool to -10 ° C for storage.

Add the above product to 100 parts by weight of dispersant-acetone, 0.5 parts by weight of styrene, 100 parts by weight of dichloroethane, and 1 part by weight of octanol, mix and disperse the grinding reaction with a titanium-based nano-metal powder grinding device for 5 hours to obtain The titanium-based nano-metal powder has a specific surface area of 9.6 m ² / g. Example 5

The mixing aid-20 parts by weight of polyamide 650 with a molecular weight of 500-800 and the protective agent-30 parts by weight of a low-viscosity chlorinated rubber are heated and mixed, and the grinding aid and the protective agent-5 parts by weight of polysiloxane are added at high speed. Stir for 1.5 hours, and then add 500 parts by weight of dispersant-toluene: xylene = 30: 70 or 50:50 mixed solvent.

Take 100 parts by weight of industrial titanium powder and 100 parts by weight of the above reaction product, and then add 500 parts by weight of dispersant-xylene, grind the reaction on a titanium-based nano-metal powder grinding device for 2 hours, and then add the dispersant-toluene to stop : Xylene = 30: 70 or 50: 50 mixed solvent with 100 parts by weight and cyclohexanone with 5 parts by weight. The reaction was continued for 2 hours to prepare a titanium-based nano metal powder with a specific surface area of 10 m ² / g.

In the above embodiment, the obtained titanium-based nano-metal powder is a titanium powder coated with an organic resin, wherein the titanium content is above 90%. It should also be noted that the particle size data of the titanium-based nano-metal powder is not given because the resulting product is in a coated form.

The present invention is not limited to the specific modes described above. Those skilled in the art can also make various changes to the present invention without departing from the spirit of the present invention and the scope of protection as claimed in the following claims. .

Claims

Profit requirements

1. A method for preparing titanium-based nano metal powder, the method includes the following two stages:

2. A method for preparing titanium-based nano metal powder according to the requirements of:

The pulverizing aid is an oligomer or polymer having unsaturated functional groups, and includes one or more of polyvinyl acetate, polyacrylate, low molecular weight polyamide, oleic acid, or polysiloxane; the The protective agent is one or more of low-molecular-weight phenol and its prepolymer, epoxy compound, sulfur-containing rubber, chlorinated rubber, polyvinyl alcohol, polyaluminum ethylsiloxane, or polysiloxane;

The dispersant is one or more of an aromatic compound, acetophenone, a hydrocarbon, a chlorohydrocarbon, an alcohol, a ketone, or an acetate.

3. The method according to claim 1, wherein in the grinding stage, the grinding temperature is 70 to 100 ° C, and the grinding time is 1-5 hours.

4. The method according to claim 1, wherein the dispersant is an alcohol of < _2- (: ₈ and a ketone of C ₃ -C ₆ .

5. A titanium-based nano metal powder prepared by the preparation method according to any one of claims 1-4, wherein the metal powder exists in a coated form, and wherein the titanium content is greater than 90% by weight, preferably 93-95% by weight.

6. A grinding device for implementing the preparation method according to any one of claims 1-4, characterized in that the main shaft (1), at least two auxiliary shafts (2), and at least two A rotating drum (3) symmetrically arranged with respect to the main shaft and a connecting device for connecting the main shaft and the auxiliary shaft. One end of the connecting device is installed on the main shaft and can rotate with the main shaft, and each rotating drum (3) is supported on its own The secondary shaft is rotated on the secondary shaft together with the secondary shaft, and the secondary shaft is supported on the other end of the connection device in a rotatable manner about the axis of the secondary shaft and can be rotated around the main shaft together with the connection device. The grinding device further includes a rotary drum (3 ) A driving device that rotates around the auxiliary shaft and revolves around the main shaft. The barrel of the rotating drum (3) contains thousands of abrasive bodies.

7. The grinding device according to claim 6, wherein the grinding device includes At least two rotating drums (3), the rotating drum (3) is connected to the auxiliary shaft (2) by means of a flange; the main shaft (1) is driven by a motor (9) to rotate, and the auxiliary shaft (2) is driven by the main shaft through a speed change device (8) (1) Drive rotation.

8. The grinding device according to claim 6, wherein the rotation speed of the main shaft (1) is set to 100-1000 rpm, and the rotation speed ratio of the main shaft (1) to the auxiliary shaft (2) is set to 1: 2 to 10.

9. The grinding device according to claim 6, wherein the aspect ratio of the rotating drum (3) is at least 10: 1.

10. The grinding device according to claim 6, wherein both ends of the rotating drum (3) are connected to the supporting layshaft (2) at both ends by means of flanges, or the rotating drum C3) itself functions as the auxiliary shaft (2) at the same time.

1 1. If the grinding device of any of 6-10 is required, the auxiliary shaft (2) is directly driven by an independent power system, and the rotation of the independent power system of each drum (3) is synchronized and the same Direction, same speed.

12. The grinding device according to any one of claims 6 to 11, wherein the diameter of the grinding body is 5 mm to 30 mm, the mass of the grinding body is 10 to 100 grams, and the mass ratio of the grinding body to the material is 1: Between 1 and 10: 1.

13. The grinding device according to any one of claims 6 to 12, wherein the grinding body can be made of different materials, including but not limited to bearing steel, special tungsten alloy, fused zirconia, agate, and nickel-based Grinding alloy, etc.

14. The grinding device according to any one of claims 6 to 13, wherein a finned radiator is installed on the rotating drum (3), or a cooling device is provided on the entire device.

15. The grinding device according to any one of claims 6 to 14, wherein the temperature of the material in the drum (3) is controlled by one of the following methods or a combination thereof:

Add cooling materials while adding materials;

Cool the material to a lower specified temperature in advance;

A cooling environment is established around the entire device. During the production process, the material heat is transmitted by the fins by the rotation of the rotating drum (3).

16. The grinding device according to claim 15, wherein the environmental temperature of the device is controlled as follows: The device is placed in a semi-enclosed environment as a whole, and the temperature-reduced and dehumidified treatment is intermittently introduced according to the environmental temperature requirements. Protective cooling gas to adjust the ambient temperature.