KR20180066347A

KR20180066347A - Method for Manufacturing Non Metallic Silicon Complex Using Nano Hole of CNT and the Silicon Complex

Info

Publication number: KR20180066347A
Application number: KR1020160166377A
Authority: KR
Inventors: 이상철
Original assignee: (주) 더웰; 이상철
Priority date: 2016-12-08
Filing date: 2016-12-08
Publication date: 2018-06-19
Also published as: KR101993883B1

Abstract

The present invention relates to a method for producing a metal-free silicon composite material using carbon nanotubes (CNT). The method comprises: a first step of mixing and heating carbon nanotubes (CNT) and silicon oil, and stirring the mixture; a second step of compressing the mixture mixed in the first step while applying heat by using an open roll to produce a plate-shaped silicon pellet; a third step of introducing solid silicon to the silicon pellet formed in the second step, and compressing the silicon pellet; a fourth step of introducing a crosslinking agent to the mixture kneaded and dispersed in the third step, and mixing the same; and a fifth step of molding the mixture mixed in the fourth step by a thermal press under a temperature of 190 to 210°C to produce a product. A silicon material of high content and low resistance (for example, 1 Ω or less) can be produced.

Description

TECHNICAL FIELD [0001] The present invention relates to a carbon nanotube-containing silicon composite material, and a method for manufacturing a carbon nanotube-

The present invention relates to a method of manufacturing a silicon composite material, and more particularly, to a method for manufacturing a metal-free silicon composite material using carbon nanotubes (CNTs) and a material thereof.

Carbon nanotubes (CNTs) have a large specific surface area of 1 to several tens nanometers (nm) in diameter and an apparent density of 0.02 to 0.05 g / cc, making it difficult to add a silicon material and a high CNT material. Also, the dispersibility was difficult due to the viscosity of the silicone material. Silicone is not bonded to the polymer resin and an organic dispersant can not be used.

Silicon is excellent in mechanical properties and chemical resistance due to silicon and oxygen bonding. However, since it has low density to add CNT material, there is a problem of workability. Therefore, it is limited to the development of anti-static and high resistance products through addition of low CNT .

(1) Patent Registration No. 10-1666881: a method for manufacturing a non-metal electroconductive CNT composite material excellent in chemical resistance and having a surface electric resistance of 1? /? Or less, a CNT pellet used in the production thereof, (2) Patent Registration No. 10-1666884: A method for producing a metal-free CNT composite material having excellent electromagnetic wave shielding property and a surface electric resistance of 1? /? Or less, and a CNT composite material produced thereby

It is an object of the present invention to make a CNT pellet using CNT nanopores to produce a silicon material having a low content of low resistance (for example, 1?). This level of low-resistance products can indeed be useful in a variety of industries.

More specifically, the object of the present invention is to prepare a CNT pellet having a low density of CNT material excellent in silicon and dispersibility, and to produce a metal-free silicon material having a resistance of 1? Or less by adding CNT to a dispersion and a high content when mixing with silicon.

Silicone has a problem in that peeling is caused when a general polymer resin, a surfactant or an organic dispersant is used. In addition, silicon may not be crosslinked smoothly with an air layer or moisture inside the silicon material, and CNTs may become more problematic due to the presence of air layer and moisture in the nano pores.

The above-

A carbon nanotube (CNT) and a silicone oil are mixed and heated while stirring;

A second step of producing a plate-shaped silicon pellet by pressing the mixture mixed by the first step while applying heat using an open roll;

A third step of introducing solid silicon into the silicon pellet formed by the second step and pressurizing the silicon pellet;

A fourth step of adding a cross-linking agent to the mixture which is kneaded and dispersed in the third step and mixing the mixture;

A fifth step of molding the mixed mixture by the fourth step with a hot press at a temperature of 190 to 210 ° C to produce a product;

The present invention provides a method for manufacturing a metal-free silicon composite material using carbon nanotubes.

In the first step, CNT pellets having a low density (0.02-0.05 g / cc) of 0.02-0.03 g / cc can be prepared and dispersed through silicon and an open roll. The viscosity of CNT nanopore is 900 ~ 1,100 so that silicone oil can be injected.

Ratio of 70 to 80% by weight of CNT and 20 to 30% by weight of silicone oil having a viscosity of 900 to 1,100; The agitation is carried out at a heating stirring temperature of 110 to 130 캜 for 20 minutes at RPM 10 and 30 minutes at RPM 50 for a total of 50 minutes. At this time, the total weight of CNT and silicone oil is 5,000 g and CNT is MWCNT. When the heating agitation temperature is in the range of 110 to 130 ° C, stirring for 40 to 60 minutes causes the moisture of the CNT nanopores to evaporate and the viscosity of the silicone oil of the CNT nanopore ranges from 900 to 1,100 at room temperature and 500 ~ 600 to be sucked into the nanopore well. Also, the volume is reduced by 60-80%, more specifically by 65-75%.

The second step is to produce CNT pellets based on silicone oil. Silicon-only CNT pellets are produced in the form of plates by pressing two rolls through an open roll. At this time, the temperatures of the two rolls are 140 to 160 ° C., and the temperature of the mixture of the CNT and the silicone oil is simultaneously carried out immediately after stirring to remove the air layer and moisture of the CNT pores using two pressing rolls.

The density of the silicon-dedicated CNT pellet produced by the second step is 0.2-0.3 g / cc and cooled to room temperature.

The third step is a step of producing a low-resistance silicon material by using solid silicon, and solid silicon having a hardness of 10 to 40 is used. If silicone having a hardness of solid silicon of 40 or more is used, the hardness becomes 85 or more at the time of pressing by hot press after crosslinking, and it may become difficult to produce.

In the fourth step, 14 to 17% by weight of CNT pellets (80% by weight of CNT and 20% by weight of silicone oil) and 86 to 83% by weight of solid silicon are mixed and stirred with a pressurized kneader. At this time, the solid silicon is first introduced, and the air layer in the silicon is removed by pressure kneading for about 10 minutes. Then, the CNT pellets are introduced and the CNTs are dispersed by pressurized kneading for an additional 15 minutes. Pressurized kneaders should be at room temperature. The low-resistance CNT compound silicon in which CNT and silicon are mixed and dispersed as an accessory kneader is passed through two rolls in the state of an open roll through the open roll to make it good to press. At this time, the temperature is changed to room temperature, 0.9 to 1.1 wt% of crosslinking agent is added to the total weight, and the mixture is dispersed evenly, and is passed through two compression rolls for 5 to 10 minutes.

In the fifth step, the mixture is pressurized in a hot press, for example, at a reference temperature of 190 to 210 DEG C for about 3 minutes to form a product.

The composite silicon material produced by the method of the present invention has excellent chemical resistance and can have a surface resistance of 1.4 to 0.3 OMEGA electrical conductivity, and can be used as a heating element, a low resistance packing, an antenna, an electrolytic product, IT, , Electromagnetic wave shielding products, hydrogen cell sticks, and the like.

More specifically, since the CNT composite material according to the present invention has an excellent electromagnetic shielding function due to its high electrical conductivity, it is particularly useful for the production of products requiring electromagnetic shielding function, and has excellent chemical resistance and excellent mechanical properties It can be applied to a wide range of products.

Further, when the core of the wire is formed by the material according to the present invention, since the core of the wire has ductility and rubber elasticity, it is possible to replace the wire of the conventional metal and to provide a moving product such as a robot, a dron, It can be applied to various fields such as tools, weapons, and communication devices.

1 is a process diagram of a method for manufacturing a metal-free silicon composite material using carbon nanotubes according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

SUMMARY OF THE INVENTION A carbon nanotube (CNT) and a silicone oil are mixed and heated while stirring; A second step of producing a plate-shaped silicon pellet by pressing the mixture mixed by the first step while applying heat using an open roll; A third step of introducing solid silicon into the silicon pellet formed by the second step and pressurizing kneading; A fourth step of adding a cross-linking agent to the mixture to be kneaded and dispersed in the third step and mixing the mixture; And a fifth step of molding the mixture mixed by the fourth step with a hot press at a temperature of 190 to 210 DEG C to produce a product.

According to the present invention, it is possible to provide a silicon composite material characterized in that carbon nanotubes are uniformly dispersed in a silicon base, and that the electrical resistance is 1?.

The present invention will be described in detail. Silicon has difficulty in dispersing carbon nanotubes (CNTs) because of the absence of other polymer and organic dispersion-bonding strength. The present invention relates to a CNT nanopore having a silicon-based viscosity of 900 to 1,100, a silicone oil, a CNT nanopore having an air layer and moisture removed therefrom, a CNT density of 0.02 to 0.05 g / g / cc. If the viscosity of the silicone oil is less than 900, the silicone oil may escape to the surface after molding. If the viscosity is more than 1,100, the injection of the CNT nanopore may become difficult.

The ratio of the CNT to the silicone oil is 20 to 30% by weight based on 70 to 80% by weight of the CNT. When the silicone oil is less than 20% by weight, the CNT nanopore oil may not be sufficiently injected. %, It is possible to escape to the surface after cross-linking with a hot press.

The CNTs and silicone oils mixed at the above ratios are first heated and stirred at a temperature of 110 to 130 ° C for 20 minutes at a RPM of 10 to reduce the initial volume by 30 to 40%. In this case, when the heating temperature is below 110 ° C, the swelling of the CNT nanopores is weak and the injection of the silicone oil is weak. Also, the viscosity of the silicone oil does not become 500 ~ 600 at a temperature of 110 ~ The oil injection of the pores is weak and the air layer in which CNT nanopores exist and moisture may not evaporate.

When the heating stirring speed is higher than RPM 10, the specific gravity of the silicone oil is larger than the specific gravity of the CNT, so that the silicone oil is only supported on the bottom surface and the CNT is difficult to disperse enough oil in the upper layer.

After the first heating stirring, the temperature is maintained at 110 ~ 130 ° C, the RPM speed is increased to 50, and the second addition is further performed for about 30 minutes. When the second additional agitation is performed for 20 to 40 minutes, the volume is reduced to 60 to 80% of the initial volume, and the next CNT pellet process can be smoothly performed.

Next, CNT pellets in the form of a plate are prepared through the two open squeeze rolls at the temperature of 150 캜 in the injected silicone oil of the CNT nano pores. At this time, the moisture and the air layer, which have not been removed in the heating stirring, are passed through two open squeeze rolls to further remove the air layer so that the water content becomes 50 ppm or less.

It is preferable that the CNT pelletization process is performed immediately after the heating stirring with the open squeeze roll. It is appropriate to make the same material three to five times in the squeeze roll passage. If the sintering is performed five times or more, the CNT density becomes 0.3 g / cc or more, / cc, which makes it difficult to work with silicon.

The CNT pellets of the judge structure were irregular in size about 1 mm in thickness and the maximum size was less than 15 mm.

In the next step, solid silicon and CNT pellets are dispersed in a room temperature state. In the pressurized kneader, the solid silicon is stirred at room temperature for about 10 minutes with a pressurized kneader to remove the air layer of solid silicon, and CNT pellets 20% by weight) and solid silicon 86 to 83% by weight, followed by dispersion for 15 minutes. The hardness of solid silicon should be about 10 to 40, and hardness of 85 or more as shown in comparative photograph 3 when 17 wt% of CNT pellets and solid silicone hardness of 40 or more is hard to form.

In the next step, 0.9 to 1.1 wt% of the crosslinking agent is added to the total weight through an open roll at room temperature to allow post-processing of the pressurized kneaded silicon CNT material at room temperature, and the crosslinking agent is dispersed through the two mixing pressing rolls . At this time, the injection time of the cross-linking agent is added at the final stage so as not to be absorbed into the CNT nanopore, and when the cross-linking agent is 0.9 wt% or less, the thermal curing time may be prolonged. After adding the cross-linking agent, the plate is passed through two open mixing squeeze rolls so that the cross-linking agent is evenly dispersed for 5 to 10 minutes to prepare a plate sheet having a thickness of 1 to 5 mm. As the crosslinking agent, TRIGONOX 101 (0.4-0.5%) may be used as a molding crosslinking agent, and ENOX DCBP (1.4%) may be used for extrusion. They may also be used at the same time.

The sheet-like sheet produced as described above can produce various types of products and can produce products by pressurizing with a hot press at a temperature of 190 to 210 캜 for 3 minutes at a reference thickness of 2 mm.

The present invention has developed an electrically conductive silicone product having a surface resistance of 1? Or less by the above-described production method, and its properties are shown in the following table.

Hardness and Resistance of Solid Silicon According to CNT Pellet Content Initial silicone hardness silicon CNT pellets Final product hardness Surface resistance (Ω / sq) 10
86 wt% 14 wt% 68 1.42Ω / □ 83 wt% 17 wt% 73 0.8Ω / □ 30
86 wt% 14 wt% 77 1.17Ω / □ 83 wt% 17 wt% 82 0.64Ω / □ 40
86 wt% 14 wt% 82 0.59 Ω / □ 83 wt% 17 wt% 87 It is difficult to mold

* ohm / sq = Ω / □ = Sheet resistance

In the table above, the surface resistance is an average after 5 measurements and the hardness is the average measured five times by Shore A Hardness Tester.

The configuration shown and described above is merely a preferred embodiment based on the technical idea of the present invention. It will be understood by those skilled in the art that various changes and modifications may be made without departing from the scope of the present invention.

Claims

A carbon nanotube (CNT) and a silicone oil are mixed and heated while stirring;
A second step of producing a plate-shaped silicon pellet by pressing the mixture mixed by the first step while applying heat using an open roll;
A third step of injecting solid silicon into the silicon pellet formed by the second step and pressurizing the silicon pellet;
A fourth step of adding a cross-linking agent to the mixture which is kneaded and dispersed in the third step and mixing the mixture;
A fifth step of molding the mixed mixture by the fourth step with a hot press at a temperature of 190 to 210 ° C to produce a product;
Wherein the carbon nanotube-based material is a carbon nanotube.

The method according to claim 1,
Wherein the mixing ratio of the carbon nanotube (CNT) to the silicone oil is 70 to 80 wt%: 20 to 30 wt%.

The method according to claim 1,
Wherein the carbon nanotube (CNT) has a density of 0.02 to 0.05 g / cc.

The method according to claim 1,
Wherein the silicon pellets have a density of 0.02 to 0.03 g / cc.

The method according to claim 1,
Wherein the mixing ratio of the silicon pellets to the solid silicon in the third step is 14 to 17 wt%: 86 to 83 wt%.

The method according to claim 1,
Wherein the first step and the second step are performed continuously without a time interval. &Lt; Desc / Clms Page number 19 >

A silicon composite material having carbon nanotubes characterized in that carbon nanotubes are uniformly dispersed in a silicon base and has an electric resistance of 1 ?.