KR101865724B1

KR101865724B1 - Preparing method for porous thermal insulation coating layer

Info

Publication number: KR101865724B1
Application number: KR1020160169390A
Authority: KR
Inventors: 김보경; 여인웅; 홍웅표; 백홍길; 노수정; 오승정; 이승구; 이승우
Original assignee: 현대자동차 주식회사
Priority date: 2016-12-13
Filing date: 2016-12-13
Publication date: 2018-06-08

Abstract

The present invention relates to a method for producing a porous heat insulating coating layer. The above manufacturing method can uniformly form a porous heat insulating coating layer having a high adhesion force in a shorter time, and such a porous heat insulating coating layer is applied to an internal combustion engine to enable low thermal conductivity and low volume heat capacity to be secured.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a porous heat insulating coating layer,

The present invention relates to a method for producing a porous heat insulating coating layer. More particularly, the present invention relates to a method of manufacturing a porous heat insulating coating layer which can secure a low thermal conductivity and a low volumetric heat capacity and can be applied to an internal combustion engine to exhibit excellent durability.

An internal combustion engine refers to an engine that directly converts combustion energy generated by combustion of fuel into heat by acting on the piston or turbine blades directly. A gas turbine, a jet engine, a rocket, and the like are internal combustion engines, although many of them refer to reciprocating engines that ignite and explode a mixture of fuel and air in the cylinder to move the piston.

Gas engines, gasoline engines, petroleum engines, diesel engines and the like are classified into fuels using internal combustion engines. Oil, gas and gasoline engines are ignited by electric sparks by ignition plugs (ignition), and diesel engines spontaneously ignite by injecting fuel into high temperature and high pressure air. There are four strokes and two stroke strokes depending on the stroke and operation of the piston.

Generally, it is known that the internal combustion engine of an automobile has a thermal efficiency of about 15% to 35%. Even in the maximum efficiency of the internal combustion engine, heat energy and exhaust gas emitted to the outside through the wall of the internal combustion engine, % Or more is consumed.

Since the efficiency of the internal combustion engine can be improved by reducing the amount of heat energy released to the outside through the wall of the internal combustion engine as described above, it is possible to install a heat insulating material on the outside of the internal combustion engine, to change the material or structure of the internal combustion engine, Were used to develop the cooling system.

Particularly, it is possible to improve the efficiency of the internal combustion engine and the fuel efficiency of the automobile by minimizing the heat generated in the internal combustion engine from being released to the outside through the wall of the internal combustion term. In the internal combustion engine, which is subjected to repeated high temperature and high pressure conditions The research on insulation materials and insulation structures that can be maintained for a long time is very limited.

Accordingly, there is a demand for the development of a new thermal insulator which has excellent low thermal conductivity and heat resistance, can be applied to an internal combustion engine and can be maintained for a long time.

An object of the present invention is to provide a method of manufacturing a porous heat insulating coating layer which can secure a low thermal conductivity and a low volumetric heat capacity and can be applied to an internal combustion engine to exhibit excellent durability.

In the present specification,

Forming a granule comprising a ceramic compound and a polymeric compound;

Spraying the granules on a substrate under vacuum to form a granular coating layer; And

A step of heat treating the substrate on which the granular coating layer is formed to form pores by removing the polymer compound

A method for manufacturing a porous heat insulating coating layer is provided.

Hereinafter, a method of manufacturing a porous heat insulating coating layer according to a specific embodiment of the present invention will be described in detail.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

The singular forms as used herein include plural forms as long as the phrases do not expressly contradict it. Also, as used herein, the term " comprises " embodies specific features, regions, integers, steps, operations, elements or components, and does not exclude the presence of other specified features, regions, integers, steps, operations, elements, It does not.

According to the research results of the present inventors, a process of coating granules containing a ceramic compound and a polymer compound on a substrate by a granule spray in vacuum (GSV) process and heat treating the granules to form pores by removing the polymer compound It was confirmed that a porous heat insulating coating layer having a high adhesion force can be formed uniformly in a shorter time. The porous heat insulating coating layer formed by this method not only enables low thermal conductivity and low volumetric heat capacity to be secured, but also exhibits excellent durability even under extreme conditions such as high temperature and high pressure, thereby achieving further improved long-term reliability.

In this connection, in the case of the composite coating using the conventional porous aerogels and the organic binder, microcracks are formed in the coating layer by thermal decomposition of the organic binder under the operating environment of the internal combustion engine and peeled off. In the case of thermal spray coating using plasma, there is a high possibility that the coating material is exposed to a high temperature and the inner pore structure of the airgel or the like is deformed, and it is difficult to obtain a coating layer having a high porosity. In addition, in the case of coating by the aerosol deposition method, uniformity of the coating layer is lowered due to agglomeration of powders during the coating process, and it is difficult to ensure the stability of the continuous process.

1, a method for preparing a porous heat insulating coating layer according to the present invention comprises preparing a granule by mixing a ceramic compound and a polymer compound, and granulating the granule by a GSV process The granular coating layer is formed by spraying, and then the granular coating layer is subjected to a heat treatment, whereby a porous heat insulating coating layer having a high adhesion force can be formed in a shorter time. In particular, the GSV process enables a homogeneous large area uniform coating, which enables high coating reliability and overall process efficiency improvement. Further, since the above-described processes are performed under mild conditions as a whole, and the pores are formed by heat treatment after forming the granular coating layer, it is possible to lower the concern about the deformation of the pore structure and to reduce the porosity of the porous heat- .

According to one embodiment of the invention,

Forming a granule comprising a ceramic compound and a polymeric compound;

A method for manufacturing a porous heat insulating coating layer is provided.

Formation of granules

According to an embodiment of the present invention, the granules may be prepared by granulating a mixture of the above compounds, which comprises a ceramic compound and a polymer compound.

The ceramic compound is a component for imparting an adiabatic effect to an arbitrary substrate, and may include at least one or more metal oxides.

Specifically, the ceramic compound may be selected from the group consisting of Si, Al, Ti, Zr, Ca, Mg, Y, , Or an oxide in which two or more metal elements are respectively bonded to oxygen. More specifically, the ceramic compound may be yttria-stabilized zirconia (YSZ) including zirconium oxide and yttria.

As the ceramic compound, a ceramic powder having an average diameter of 1 占 퐉 to 50 占 퐉 may be used. The method of obtaining the ceramic powder is not particularly limited and may be carried out by using a known milling method such as a ball mill.

The polymer compound is a component that is mixed with the ceramic compound to form granules, then coated on the substrate, and finally removed from the granule coating layer by heat treatment to provide pores in the vacant space.

The polymeric compound may be selected from the group consisting of polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene (ETFE), tetrafluoroethylene-chlorotrifluoroethylene copolymer (TFE / CTFE), ethylene-chlorotrifluoroethylene (ECTFE), polyethylene, polystyrene, may include at least one compound selected from the group consisting of poly (methyl methacrylate), poly (ethylene oxide), poly (vinyl alcohol), and polyamide .

In particular, the polymer compound is preferably polytetrafluoroethylene in order to increase the efficiency of the heat treatment process and prevent deformation of the pores in the process, as a component which is removed by heat treatment after formation of the granular coating layer.

The method of forming the granules containing the ceramic compound and the polymer compound is not particularly limited and may be carried out by applying a known granulation method such as fluidized bed granulation or dry granulation. In forming the granules, a suitable solvent may be used if necessary, and a step of drying the formed granules may be further performed.

At this time, the content of the ceramic compound and the polymer compound forming the granules can be determined in consideration of the components of each compound and the porosity to be imparted to the porous heat-insulating coating layer. However, if the content of the polymer compound is too low, it may be difficult to secure a sufficient porosity. On the other hand, if the content of the polymer compound is too high, it may be difficult to ensure sufficient heat insulation and the coating layer may easily peel off.

Accordingly, it is preferable that the granules contain 80 to 99.9% by weight of the ceramic compound and 0.1 to 20% by weight of the polymer compound. More preferably, the granules may comprise 85 to 99.9% by weight of the ceramic compound and 0.1 to 15% by weight of the polymeric compound.

The size of the granules can be determined in consideration of the efficiency of the process of granulating the granules by the GSV process and the uniformity of the coating layer. However, if the size of the granules is too small, it may be difficult to secure a sufficient porosity. On the other hand, if the size of the granules is too large, it is difficult to realize sufficient adhesion to the substrate and it may be difficult to form a uniform coating layer. Therefore, it is preferable that the granules have an average diameter of 50 mu m to 500 mu m or 50 mu m to 200 mu m. Here, the average diameter of the granules means the number average diameter based on the longest diameter of the granules.

Formation of Granular Coating Layer

According to one embodiment of the invention, the step of forming the granular coating layer may be performed by a method of spraying the granules on a substrate under vacuum, for example, a granule spray in vacuum (GSV) process.

The GSV process is a process of forming a dense granular coating layer by colliding the granules on a substrate using a pressure difference. Such a GSV process enables formation of a coating layer exhibiting uniform characteristics while allowing stable process operation under mild atmosphere compared to thermal spray coating or aerosol deposition method.

Specifically, the step of forming the granular coating layer by the GSV process includes the steps of: supplying the granules to the injection nozzle by compressed air; And injecting the supplied granules through the injection nozzle onto the substrate provided in the vacuum chamber. For this purpose, the step of forming the granular coating layer includes a vacuum chamber equipped with a substrate mounting means, a vacuum pump for maintaining a vacuum atmosphere in the vacuum chamber, a spray nozzle for spraying the prepared granules together with compressed air into the vacuum chamber, An apparatus including a granular feeder for delivering the prepared granules to the injection nozzle may be used.

The substrate is any object covered by the porous heat-insulating coating layer, and according to an embodiment of the invention, the inner surface of the internal combustion engine or the parts of the internal combustion engine and the like are exemplified.

Said spraying may be carried out at a distance of 5 to 200 mm, or 10 to 200 mm, or 10 to 150 mm away from said substrate. If the spray distance is too short, the coating area may be narrow and the process efficiency may be decreased. On the other hand, if the ejection distance is excessively long, the collision energy of the granules with respect to the substrate is not sufficient and the adhesion of the coating layer may be deteriorated.

The flow rate of the compressed air and the internal pressure of the vacuum chamber can be determined in consideration of the pressure difference that ensures sufficient collision energy of the granules. Specifically, the compressed air can be supplied into the vacuum chamber through the injection nozzle at a flow rate of 20 to 50 L / min, or 25 to 40 L / min, or 30 to 35 L / min together with the granules. The inside of the vacuum chamber may be maintained in a vacuum atmosphere of 1 to 50 torr, 1 to 25 torr, or 5 to 15 torr.

On the other hand, the granular coating layer may be formed to have a thickness of 10 μm to 2000 μm, or 20 μm to 1000 μm, or 20 μm to 500 μm, or 30 μm to 300 μm. If the thickness of the granular coating layer is less than 10 탆, the density of the final porous heat-insulating coating layer can not be sufficiently lowered, so that it may be difficult to lower the thermal conductivity to an appropriate level or less and the protective function of the substrate surface may be deteriorated. On the other hand, if the thickness of the granular coating layer exceeds 2000 탆, cracks may be generated in the final porous heat-insulating coating layer, which is not preferable.

Steps of pore formation

According to an embodiment of the present invention, the step of forming the pores may be performed by a method of removing the polymeric compound from the granular coating layer by heat treating the substrate on which the granular coating layer is formed.

That is, by the heat treatment, the polymer compound is removed from the granular coating layer and pores are formed in the vacant space, so that the porous heat insulating coating layer according to an embodiment of the present invention can be provided.

Specifically, the heat treatment may be carried out by heating the substrate on which the granular coating layer is formed at a temperature at which the polymer compound can be carbonized, for example, at a temperature of 300 to 500 ° C.

Here, the time at which the heat treatment is performed may include consideration of the shape of the substrate, the type of the polymer compound contained in the granule, the thickness of the granule coating layer, the temperature of the heat treatment, and the porosity to be imparted to the final porous heat- Lt; / RTI >

The heat treatment may be performed so that the porous heat insulating coating layer has a porosity of 30% or more, 40% or more, 50% or more, or 65% or more. If the porosity of the porous heat insulating coating layer is less than 30%, it may be difficult to realize proper heat insulating properties. The porosity of the porous heat insulating coating layer means the ratio of all the pores contained in the porous heat insulating coating layer. For example, the porosity may be a percentage of the area occupied by the pores with respect to the total area of the cross-section in one cross-section of the porous heat-insulating coating layer.

For reference, the granules used for forming the granular coating layer contain not more than 20% of the polymeric compound, but the polymeric compound has a lower density than the ceramic compound, so that it can exhibit a high porosity. However, the porosity is not determined only by the amount of the polymer compound contained in the granules, but is also influenced by the coating yield in the GSV process.

The porous heat insulating coating layer obtained by the above steps can have low thermal conductivity and low volumetric heat capacity.

Specifically, the porous heat insulating coating layer has a density of 2.0 W / mK or less, or 1.5 W / mK or less, or 1.0 W / mK or less, or 0.1 to 1.0 W / mK, or 0.3 to 0.7 W / mK (measured according to ASTM E1461) Can be expressed.

The thermal conductivity refers to the degree of the ability of a material to transmit heat by conduction. Generally, the lower the thermal conductivity, the slower the transfer of thermal kinetic energy and the better the thermal insulation. When the thermal conductivity of the porous heat insulating coating layer is more than 2.0 W / mK, the thermal kinetic energy is transmitted too fast, so that the amount of heat energy released to the outside of the porous heat insulating coating layer is increased to decrease the heat insulating property, .

The porous heat insulating coating layer may have a specific surface area of 3000 kJ / m ³ K or less, or 2500 kJ / m ³ K or less, or 2300 kJ / m ³ K or 1000 2300 kJ / m ³ K, Or a volumetric heat capacity of 1000 to 2050 kJ / m < ³ > K. The volumetric heat capacity means a quantity of heat required to raise the unit volume of the material by 1 DEG C, and can be obtained by the following equation (1).

[Equation 1]

Volume heat capacity (kJ / m ³ K) = specific heat (kJ / g * K) x density (g / m ³ )

Therefore, if the volume heat capacity of the porous heat insulating coating layer is excessively increased to more than 3000 kJ / m ³ K, the density of the porous heat insulating coating layer becomes large and the thermal conductivity also increases, and it may be difficult to obtain the desired heat insulating property.

The porous heat insulating coating layer may exhibit a density of 4.5 g / ml or less, or 0.5 to 4.5 g / ml, or 1.0 to 4.0 g / ml, or 2.5 to 4.0 g / ml, measured according to ISO 18754.

If the density of the porous heat insulating coating layer is more than 4.5 g / ml, the thermal conductivity and volumetric heat capacity of the porous heat insulating coating layer can not be lowered to an appropriate level, and the heat insulating effect may be reduced. On the other hand, if the density of the porous heat insulating coating layer is less than 0.5 g / ml, the mechanical properties such as weather resistance of the porous heat insulating coating layer may be poor.

The method of manufacturing a porous heat insulating coating layer according to the present invention can uniformly form a porous heat insulating coating layer having a high adhesion force in a shorter time. The porous heat insulating coating layer formed in this manner not only ensures low thermal conductivity and low volumetric heat capacity but also exhibits excellent durability even under extreme conditions such as high temperature and high pressure, thereby securing an improved long-term reliability.

1 is a process flow diagram illustrating a method for manufacturing a porous heat insulating coating layer according to an embodiment of the present invention.
Fig. 2 is an FE-SEM image of the surface of the porous heat-insulating coating layer obtained in Example 1. Fig.
3 is an FE-SEM image of the surface of the porous heat-insulating coating layer obtained in Example 2. Fig.
4 is an FE-SEM image of the surface of the porous heat-insulating coating layer obtained in Example 3. Fig.
5 is an FE-SEM image of the surface of the coating layer obtained in Comparative Example 1. Fig.
6 is an FE-SEM image of the surface of the coating layer obtained in Comparative Example 2. Fig.
7 is an FE-SEM image of the surface of the coating layer obtained in Comparative Example 3. Fig.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the function and effect of the invention will be described in more detail with reference to specific examples of the invention. However, this is provided as an example of the invention, and thus the scope of the invention is not limited in any sense.

Example One

(1) Preparation of granules

: 1000 g of yttria stabilized zirconia (YSZ, average diameter of about 23 탆) and 10 g of polytetrafluoroethylene (PTFE, weight average molecular weight of about 23,000) were added to water and mixed. At this time, the content of the solid content in the mixture was about 50% by volume.

Thereafter, the mixture was sprayed on a disk having a rotation speed of about 10,000 rpm by using a nozzle to form spherical droplets. The spherical droplets were dried by applying hot air at 180 DEG C to obtain granules having an average diameter of about 56 mu m.

(2) Formation of granular coating layer

: A granule coating layer was formed on a substrate specimen for an internal combustion engine by a granule spray in vacuum (GSV) process using the above granules. The GSV process includes a vacuum chamber equipped with substrate mounting means, a vacuum pump for maintaining a vacuum atmosphere in the vacuum chamber, an injection nozzle for injecting the prepared granules together with compressed air into the vacuum chamber, and a granule prepared in the injection nozzle Lt; RTI ID = 0.0 > feeder < / RTI >

In this apparatus, the granules provided in the granule feeder were supplied to the injection nozzle by compressed air, and the granules supplied were injected through the injection nozzle onto the substrate specimen provided in the vacuum chamber to form granule coating layers .

At this time, the inside of the vacuum chamber was maintained in a vacuum atmosphere of 5 torr. The injection proceeded at a distance of 10 mm from the substrate specimen. The compressed air was injected into the vacuum chamber together with the granules at a flow rate of 30 L / min.

(3) Formation of pores

: The base material specimen having the granular coating layer formed was heated at a temperature of 450 캜 for 6 hours to form pores in the granular coating layer. Finally, a base material specimen having a porous heat insulating coating layer having a thickness of about 135 탆 was obtained.

Example 2

A substrate specimen having a porous heat insulating coating layer having a thickness of about 198 탆 was obtained in the same manner as in Example 1, except that the content of polytetrafluoroethylene was adjusted to 50 g in the granulation step.

Example 3

A substrate specimen having a porous heat insulating coating layer having a thickness of about 220 탆 was obtained in the same manner as in Example 1, except that the polytetrafluoroethylene was adjusted to 100 g in the granulation preparation step.

Comparative Example One

A substrate specimen having a granule coating layer having a thickness of about 98 탆 was obtained in the same manner as in Example 1 except that polytetrafluoroethylene was not added in the step of producing granules (however, the pore formation step was not carried out).

Comparative Example 2

A granule coating layer having a thickness of about 153 占 퐉 was prepared in the same manner as in Example 1 except that zirconia (average diameter of about 23 占 퐉) was used instead of yttria-stabilized zirconia and polytetrafluoroethylene was not added in the step of producing granules So that a formed substrate specimen was obtained (however, the pore formation step was not carried out).

Comparative Example 3

(1) Preparation of granules

Then, the granules were heated at 450 캜 for 6 hours to remove PTFE.

(2) Formation of granular coating layer

: A base specimen having a granular coating layer having a thickness of about 103 탆 was obtained in the same manner as in Example 1, except that the PTFE-removed granules were applied to the GSV process.

Test Example

1. FE-SEM

: The surface or cross section of the coating layer of the base specimen according to Examples 1 to 3 and Comparative Examples 1 to 3 was observed using a field emission scanning electron microscope (FE-SEM, HITACHI S-4700, HITACHI, JAPAN) , And the results are shown in Fig. 2 to Fig.

2. Thermal conductivity (W / mK)

: The thermal conductivity of the coating layer obtained in the above Examples and Comparative Examples was measured according to ASTM E1461 using a laser flash method at room temperature and atmospheric pressure, and the results are shown in Table 1 below.

3. Volume Thermal Capacity (kJ / m ³ K)

: According to ASTM E1269, the coating layer obtained in the above Examples and Comparative Examples was measured for specific heat by using a DSC apparatus at room temperature under the reference of sapphire as a reference, and the heat capacity was measured.

4. Density (g / ml)

: The density of the coating layer obtained in the above Examples and Comparative Examples was measured according to ISO 18754, and the results are shown in Table 1 below.

division Thermal conductivity (W / mK) Volume Thermal Capacity (kJ / m ³ K) Density (g / ml) Example 1 0.698 2015 3.95 Example 2 0.533 1458 3.29 Example 3 0.328 1128 2.84 Comparative Example 1 0.930 3012 5.27 Comparative Example 2 1.359 3576 5.37 Comparative Example 3 1.235 2371 4.98

Claims

Forming granules consisting of 80 to 99.9% by weight of yttria-stabilized zirconia having an average diameter of 1 [mu] m to 50 [mu] m and 0.1 to 20% by weight of polytetrafluoroethylene;
Supplying the granules to the spray nozzle by compressed air; And
Spraying the supplied granules under vacuum over the substrate provided in the vacuum chamber through the spray nozzle at a distance of 5 mm to 200 mm from the substrate to form a granular coating layer; And
Heating the substrate on which the granular coating layer is formed to a temperature of 300 to 500 ° C to form pores by removing the polytetrafluoroethylene
Wherein the porous heat-insulating coating layer comprises a porous insulating coating layer.

delete

The method according to claim 1,
Wherein the granules have an average diameter of from 50 mu m to 500 mu m.

delete

The method according to claim 1,
Wherein the compressed air is supplied at a flow rate of 20 to 50 L / min, and the vacuum chamber is maintained in a vacuum atmosphere of 1 to 50 torr.

The method according to claim 1,
Wherein the granular coating layer has a thickness of from 10 占 퐉 to 2000 占 퐉.

delete

The method according to claim 1,
Wherein the porous heat insulating coating layer has a density of 4.5 g / ml or less, which is measured in accordance with ISO 18754.

The method according to claim 1,
Wherein the porous heat insulating coating layer has a thermal conductivity of 1.0 W / mK or less as measured according to ASTM E1461.

The method according to claim 1,
Wherein the porous heat insulating coating layer has a volumetric heat capacity of 3000 kJ / m < ³ > K or less as measured according to ASTM E1269.

The method according to claim 1,
Wherein the substrate is a part of an internal surface of an internal combustion engine or an internal combustion engine.