BACKGROUND
Field of the Invention
[0001] This invention relates to a method for forming a heat insulating film, and a structure
of a heat insulating film.
Background Art
[0002] A method for forming a heat insulating film in an umbrella portion of an engine valve
has already been disclosed in Japanese Patent Laid-Open No.
2013-014830. Specifically, the aforementioned conventional method includes a first step of forming
an aluminum plating film over the entire circumference of an engine valve, a second
step of, after formation of the aluminum plating film, subjecting the entire circumference
of the engine valve to an anodic oxidation treatment to form an anodic oxidation coating
film, and a third step of, after formation of the anodic oxidation coating film, subjecting
an umbrella portion of the engine valve to a sealing treatment to form a sealing coating
film. According to this conventional method, a heat insulating film can be obtained
that has a structure in which a sealing coating film is formed on an anodic oxidation
coating film. Further, according to the engine valve on which the above described
heat insulating film is formed, in addition to improving the heat resistance and a
heat insulating property of a combustion chamber of the engine, a heat radiation property
can also be improved.
[0004] In this connection, when performing anodic oxidation treatment of an aluminum alloy,
there is the problem that because the formation of the anodic oxidation coating film
is affected by inclusions that are included in the aluminum alloy, the surface of
the anodic oxidation coating film that is formed is not smooth, and minute concavities
and convexities arise thereon. This problem can also arise in a similar manner in
the aforementioned first and second steps in a case where an aluminum alloy plating
film is formed on the surface of the engine valve and the plating film is thereafter
subjected to an anodic oxidation treatment.
[0005] When concavities and convexities arise on the surface of an anodic oxidation coating
film, a heat transfer area thereof increases. If the heat transfer area increases,
an effect of improving the heat insulating property that is obtained by the anodic
oxidation coating film is weakened. If concavities and convexities have arisen on
the surface of the anodic oxidation coating film, the fluidity of a flame that arises
inside the combustion chamber decreases, and the combustion efficiency deteriorates.
In this respect, by forming the sealing coating film in the above described third
step, the surface of the heat insulating film having a structure in which the anodic
oxidation coating film and the sealing coating film are formed can be made smooth
to a certain extent. Ideally, it is desirable for the surface of the heat insulating
film to be made as smooth as the surface of the aluminum alloy prior to the anodic
oxidation treatment.
[0006] In this connection, the sealing coating film is formed by subjecting a sealing material
that is the raw material of the sealing coating film to a drying and baking process.
Consequently, in order to make the surface of the heat insulating film smooth by means
of the sealing coating film, it is necessary to provide a large amount of the sealing
material in concave portions of the surface of the anodic oxidation coating film to
thereby make the sealing material thick at such concave portions. However, because
the sealing material contains a solvent, the thicker the sealing material, the more
difficult it becomes for a gas of the solvent that is generated at the time of drying
and baking to escape to the outside. Therefore, there is the problem that cracks are
liable to arise in the sealing coating film. Consequently, there is a trade-off relationship
between thickening the sealing material to smoothen the surface of the heat insulating
film, and reducing cracks in the sealing coating film, and it is difficult to achieve
both a smooth surface and a reduction in the amount of cracks in a compatible manner.
SUMMARY
[0007] The present invention has been conceived in view of the above described problem.
That is, an object of the present invention is, with respect to a heat insulating
film having a structure in which a sealing coating film is formed on the surface of
an anodic oxidation coating film, to smooth the surface of the heat insulating film
and also reduce the occurrence of cracks in the sealing coating film in a compatible
manner.
[0008] A first aspect of the present invention is a method for forming a heat insulating
film, including:
a step of subjecting an aluminum alloy constituting a surface of a base material to
an anodic oxidation treatment to form an anodic oxidation coating film having a surface
in which pores are formed;
a step of coating on the surface of the anodic oxidation coating film a sealing material
that includes a silicon-based polymer solution and particles of a heat insulating
material that are dispersed in the silicon-based polymer solution and are particles
having an average particle diameter that is larger than an average pore diameter of
the pores; and
a step of drying and baking the sealing material to form a sealing coating film.
[0009] A second aspect of the present invention is in accordance with the first invention,
wherein the particles may be particles that have a hollow structure.
[0010] Further, in a third aspect of the present invention, an average primary particle
diameter of the particles may be greater than 30 mn.
[0011] A fourth aspect of the present invention is a structure of a heat insulating film
that is formed by a formation method according to any one of the first to third inventions,
and may include:
an aluminum alloy constituting a surface of a base material;
an anodic oxidation coating film that is formed on a surface of the aluminum alloy,
and that has a surface in which pores are formed; and
a sealing coating film that is formed so as to cover an opening portion of the pores,
and that includes particles of a heat insulating material having an average particle
diameter that is larger than an average pore diameter of the pores.
[0012] A fifth aspect of the present invention is in accordance with the fourth invention,
wherein:
the particles may be particles that have a hollow structure; and
a porosity of the sealing coating film may be from 27.3 to 57.7%.
[0013] According to the first aspect of the present invention, a sealing treatment can be
performed using a sealing material that includes a silicon-based polymer solution
and particles of a heat insulating material that are dispersed in the silicon-based
polymer solution and are particles having an average particle diameter that is larger
than an average pore diameter of pores of an anodic oxidation coating film. In the
case of using a sealing material including particles of a heat insulating material
of the aforementioned size, the occurrence of cracks in a drying and baking process
can be suppressed in comparison to when using a sealing material that does not include
the particles. Therefore, the occurrence of cracks can be suppressed even when a sealing
material is made thicker by providing a large amount thereof on concave portions of
the surface of an anodic oxidation coating film. Further, the surface of the heat
insulating film can be made smooth by means of a thick sealing coating film that is
formed by drying and baking of the sealing material.
[0014] According to the second aspect of the present invention, since a heat insulating
function of air inside particles that have a hollow structure can be utilized, a heat
insulating film can be formed that has a high heat insulating property in comparison
to a heat insulating film that does not include particles that have a hollow structure.
[0015] According to the third aspect of the present invention, a heat insulating film that
has a high heat insulating property can be formed by using particles which have an
average primary particle diameter that is greater than 30 nm.
[0016] According to the fourth aspect of the present invention, since a sealing coating
film is provided that is formed so as to cover an opening portion of pores of an anodic
oxidation coating film, a structure of a heat insulating film having a high heat insulating
property can be provided that utilizes a heat insulating function of air inside the
pores that is located at a deeper place than the opening portion.
[0017] According to the fifth aspect of the present invention, a structure of a heat insulating
film having a high heat insulating property that is obtained by means of a sealing
coating film in which the porosity is between 27.3 and 57.7% can be provided.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018]
Fig. 1 is a flowchart for describing an embodiment of a method for forming a heat
insulating film of the present invention;
Fig. 2 is a vertical cross-sectional view of an anodic oxidation coating film;
Fig. 3 is a partially enlarged schematic view of the anodic oxidation coating film
shown in Fig. 2;
Fig. 4 is a vertical cross-sectional view of a heat insulating film formed by the
formation method of the embodiment;
Fig. 5A is a cross-sectional view of a heat insulating film formed using a sealing
material that does not include hollow silica particles;
Fig. 5B is a cross-sectional view of a heat insulating film formed using a sealing
material that does not include hollow silica particles;
Fig. 6A is a view illustrating a process for forming a sealing coating film shown
in Fig. 5;
Fig. 6B is a view illustrating a process for forming a sealing coating film shown
in Fig. 5;
Fig. 6C is a view illustrating a process for forming a sealing coating film shown
in Fig. 5;
Fig. 7 is a view for describing the periphery of a combustion chamber to which a structure
of a heat insulating film of the present invention is applied;
Fig. 8 is a partially enlarged schematic view of the heat insulating film shown in
Fig. 7;
Fig. 9 is a view showing results of measuring a thermal conductivity λ;
Fig. 10 is a view showing results of measuring a volumetric heat capacity C; and
Fig. 11 is a view showing results of measuring a surface roughness Ra.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0019] Hereunder, an embodiment of a method for forming a heat insulating film and of a
structure of a heat insulating film according to the present invention will be described
referring to Fig. 1 to Fig. 11. Note that, for each of the drawings, the same or corresponding
portions are denoted by the same reference numerals, and a description of such portions
is simplified or omitted.
[Method for forming heat insulating film]
[0020] First, an embodiment of the method for forming a heat insulating film of the present
invention will be described. Fig. 1 is a flowchart for describing the embodiment of
the method for forming a heat insulating film. In the present embodiment, first, an
anodic oxidation coating film is formed on the surface of an aluminum alloy by subjecting
a base material to an anodic oxidation treatment (step S1). In the present step, a
treatment apparatus (not illustrated) that includes a flow channel through which an
electrolytic solution is circulated and a pair of electrodes is used. Further, in
the present step, a base material is used that is made of aluminum alloy. However,
instead of a base material made of aluminum alloy, a base material may be used in
which an aluminum alloy plating film is formed on a surface such as heat-resisting
steel, carbon steel, or a titanium material.
[0021] In step S1, specifically, the aforementioned base material is placed in the aforementioned
treatment apparatus, and a voltage is applied between the aforementioned pair of electrodes
while circulating an electrolytic solution through the aforementioned flow channel.
By this means, an anodic oxidation coating film is formed on the surface of the base
material. The anodic oxidation coating film is a coating film of porous alumina that
has a large number of pores that open at the surface thereof (described in detail
later). By means of this porous structure, the anodic oxidation coating film realizes
a low thermal conductivity and a low heat capacity per unit volume (described in detail
later).
[0022] However, the surface of the anodic oxidation coating film is rough in comparison
to the surface of the base material before the anodic oxidation treatment. Fig. 2
is a vertical cross-sectional view of the anodic oxidation coating film. As shown
in Fig. 2, concavities and convexities have arisen on the surface of an anodic oxidation
coating film 10, and a surface roughness (arithmetic mean roughness) Ra thereof is
an average of 4 to 5 µm. The reason concavities and convexities arise on the surface
of the anodic oxidation coating film 10 is that inclusions that are contained in the
aluminum alloy affect the formation of the anodic oxidation coating film 10. One object
of steps S2 and S3 that are described hereunder is to smooth the surface of a heat
insulating film in which the anodic oxidation coating film 10 is a constituent element.
[0023] The description of the present embodiment will now be continued referring again to
Fig. 1. After step S1, a sealing material is coated onto the surface of the anodic
oxidation coating film (step S2). In the present step, a sealing material is used
that includes a silicon-based polymer solution that includes silicon in a main chain
backbone (more specifically, a polymer solution including polysilazane or polysiloxane
and an ether-based solvent), and silica particles that are dispersed in the silicon-based
polymer solution. The polymer solution may include an additive as necessary. A dispersant
that enhances the dispersibility of the particles, a leveling agent, a surfactant,
a viscosity modifier and the like may be mentioned as examples of the additive. The
silica particles used in the present step have an average primary particle diameter
(average particle diameter before the particles agglomerate and become secondary particles)
that is larger than an average pore diameter of pores of the anodic oxidation coating
film, and the silica particles also have a hollow structure. However, silica particles
with a solid structure may be used instead of the silica particles with a hollow structure
(hereunder, referred to as "hollow silica particles"), and particles of a heat insulating
material other than silica (for example, alumina (Al
2O
3), zirconia (ZrO
2), or titania (TiO
2) particles) may also be used. Further, two or more kinds among the aforementioned
three kinds of particles may be used at the same time.
[0024] The average pore diameter of the pores of the anodic oxidation coating film is approximately
30 nm. Therefore, in the present step, hollow silica particles for which the average
primary particle diameter is greater than 30 nm (preferably, 50 nm) are used. However,
a target value of the surface roughness Ra of the heat insulating film that is formed
by the present embodiment is approximately 1 µm, and therefore in the present step
hollow silica particles are used with respect to which an average secondary particle
diameter is less than 1 µm (preferably 500 nm, more preferably 150 nm).
[0025] Here, the term "average pore diameter" refers to an arithmetic mean diameter that
is determined by photographing sectional images at a plurality of magnifications using
a scanning electron microscope and digitalizing the obtained images by a scanner input
method, and thereafter calculating a distribution of diameters of circles having an
area that is equal to the area of respective pores extracted by computer image analysis.
Further, the term "average primary particle diameter" refers to an arithmetic mean
diameter that is determined by photographing transparent particle images at a plurality
of magnifications using a transmission electron microscope and digitalizing the obtained
images by a scanner input method, and thereafter calculating a distribution of diameters
of circles having an area that is equal to a projected area of respective pores extracted
by computer image analysis. Furthermore, the term "average secondary particle diameter"
refers to an average particle diameter (D50 value) that is obtained by a dynamic scattering
method, and is a diameter that can be simply measured by a commercially available
particle size analysis and measurement apparatus.
[0026] The mixing ratio of the hollow silica particles in the sealing material is appropriately
adjusted in accordance with the target value (for example, a value in a range from
27.3% to 57.7%) of the porosity of the sealing coating film to be formed after drying
and baking of the sealing material (after step S3).
[0027] The surface of the anodic oxidation coating film after application of the sealing
material will now be described referring to Fig. 3. Fig. 3 is a partially enlarged
schematic view of the anodic oxidation coating film 10 shown in Fig. 2. As shown in
Fig. 3, the anodic oxidation coating film 10 is constituted by alumina 10a having
a nonuniform length in a perpendicular direction relative to the surface of the aluminum
alloy, and pores 10b. Further, a sealing material 12 constituted by a silicon-based
polymer solution 14 and hollow silica particles 16 is provided so as to cover an opening
portion 10c of the pores 10b. A large amount of the sealing material 12 is provided
at concave portions of the surface of the anodic oxidation coating film 10, and a
small amount of the sealing material 12 is provided at protruding portions of the
anodic oxidation coating film 10.
[0028] The description of the present embodiment will now be continued referring again to
Fig. 1. A method for coating the sealing material in step S2 is not particularly limited,
and examples thereof include a spray method, a blade coating method, a spin coating
method, and a brush application method.
[0029] After step S2, the sealing material is dried and baked to form a sealing coating
film (step S3). The conditions (temperature, time period and the like) at the time
of drying and baking are appropriately adjusted in accordance with the thickness of
the sealing material that was coated onto the surface of the anodic oxidation coating
film. A heat insulating film is formed by performing the present step. Fig. 4 is a
vertical cross-sectional view of a heat insulating film that is formed by the formation
method of the present embodiment. As shown in Fig. 4, a sealing coating film 20 constituted
by hollow silica particles 16 and silica 18 derived from a silicon-based polymer is
formed on the surface of the anodic oxidation coating film 10. A heat insulating film
22 is constituted by the anodic oxidation coating film 10 and the sealing coating
film 20. A surface roughness Ra of the heat insulating film 22 is equal to or less
than 1 µm. The details of the structure of the heat insulating film 22 as well as
the effects obtained by the structure of the heat insulating film 22 will be described
later.
[0030] The effects of the present embodiment will now be described referring to Figs. 5A
to 6C. Heat insulating films 30a and 30b shown in Figs. 5A and 5B are heat insulating
films that were formed for the purpose of comparison with the heat insulating film
22. The heat insulating film 30a is constituted by a sealing coating film 32a that
does not include hollow silica particles, and the anodic oxidation coating film 10.
The heat insulating film 30b shown in Fig. 5B is constituted by a sealing coating
film 32b that does not include hollow silica particles, and the anodic oxidation coating
film 10. The thickness of the sealing coating film 32b is greater than the thickness
of the sealing coating film 32a, and is approximately equal to the thickness of the
sealing coating film 20 in Fig. 4. However, cracks 34 have arisen in the sealing coating
film 32b.
[0031] Fig. 6A is a view illustrating a process for forming the sealing coating film 32a.
Fig. 6B and Fig. 6C are views illustrating a process for forming the sealing coating
film 32b. In a case where a sealing material 36a that does not include hollow silica
particles is thinly coated (Fig. 6A), a drying rate of an upper part (surface part)
of the sealing material 36a at the time of drying and baking is approximately equal
to a drying rate of an inner part of the sealing material 36a. Consequently, gas of
a solvent that is generated during drying and baking is released from the inner part
of the sealing material 36a to the outside thereof. In contrast, in a case where a
sealing material 36b that does not include hollow silica particles is thickly coated
(Fig. 6B), the upper part of the sealing material 36b hardens before the inner part
of the sealing material hardens. Consequently, gas of a solvent that is generated
during drying and baking cannot escape from the inner part of the sealing material
36b, and cracks 34 arise in the sealing coating film 32b (Fig. 6C).
[0032] As will be understood from Figs. 5A to 6C, in the case of using a sealing material
that does not include hollow silica particles, there is the problem that the thicker
the coating of the sealing material, the easier it is for cracks to arise in the sealing
coating film during drying and baking (Fig. 5B, Fig. 6B and Fig. 6C). Further, when
the sealing material is thinly coated, since a thin sealing coating film is formed,
the surface of the heat insulating film cannot be smoothed sufficiently (Fig. 5A and
Fig. 6A). In contrast, according to the present embodiment, since the sealing material
including hollow silica particles of the above described size is used, the gas of
a solvent that is generated during drying and baking can be released from inside the
sealing material to the outside. The fact that it is easy for the gas of the solvent
that is generated inside the sealing material to flow along the surface of the hollow
silica particles to move to the upper part of the sealing material may be mentioned
as one of the reasons why the gas of the solvent can be released. Accordingly, in
a case where the sealing material is thickly coated also, the generation of cracks
can be favorably suppressed. Hence, a thick sealing coating film can be formed and
the surface of the heat insulating film can be smoothed.
[Structure of heat insulating film]
[0033] Next, an embodiment of the structure of a heat insulating film according to the present
invention will be described. The structure of a heat insulating film of the present
invention is applied to an inner wall of a combustion chamber of an engine. Fig. 7
is a view for describing the periphery of a combustion chamber to which the structure
of a heat insulating film of the present invention is applied. Note that although
Fig. 7 is described on the premise that the engine is a spark-ignition type engine,
the structure of a heat insulating film of the present invention can also be applied
to a compression-ignition type engine.
[0034] A cylinder 42 of an engine 40 is formed inside a cylinder block 44. A cylinder liner
46 is provided at an inner circumferential face of the cylinder 42. Further, inside
the cylinder 42, a piston 48 is slidably disposed with respect to the cylinder liner
46. A cylinder head 50 is installed at an upper portion of the cylinder block 44.
An intake port 52 and an exhaust port 54 are formed in the cylinder head 50. An intake
valve 56 is provided in the intake port 52, and an exhaust valve 58 is provided in
the exhaust port 54.
[0035] A space that is surrounded by an inner circumferential face of the cylinder liner
46, a top face of the piston 48, a bottom face of the cylinder head 50, a bottom face
of an umbrella portion of the intake valve 56 and a bottom face of an umbrella portion
of the exhaust valve 58 corresponds to a combustion chamber 60. That is, an inner
wall of the combustion chamber 60 is constituted by the inner circumferential face
of the cylinder liner 46, the top face of the piston 48, the bottom face of the cylinder
head 50, the bottom face of the umbrella portion of the intake valve 56 and the bottom
face of the umbrella portion of the exhaust valve 58. The heat insulating film 22
formed by the above described method is provided on the inner wall of the combustion
chamber 60.
[0036] Fig. 8 is a partially enlarged schematic view of the heat insulating film 22 shown
in Fig. 7. As shown in Fig. 8, the heat insulating film 22 has a structure that includes
the anodic oxidation coating film 10 and the sealing coating film 20. The anodic oxidation
coating film 10 is constituted by the alumina 10a and the pores 10b. The sealing coating
film 20 is constituted by the hollow silica particles 16 and the silica 18, and is
formed so as to cover the opening portions 10c.
[0037] The silica 18 has a lower thermal conductivity than the aluminum alloy, and has a
lower heat capacity per unit volume (volumetric heat capacity) than the aluminum alloy.
Further, the alumina 10a has a lower thermal conductivity and a lower volumetric heat
capacity than not only the aluminum alloy, but also than a conventional ceramic-based
heat insulation material. Therefore, by applying the structure of the heat insulating
film 22, in addition to improving the heat resistance and the heat insulating property
of the combustion chamber 60, a heat radiation property thereof can also be improved.
[0038] Further, according to the structure of the heat insulating film 22 including the
hollow silica particles 16 of the above described size, the heat insulating property
of the combustion chamber 60 can be further improved. The reason for this will now
be described in detail referring to Fig. 9 to Fig. 11. Fig. 9 is a view showing results
of measuring a thermal conductivity λ of two kinds of heat insulating films. Fig.
10 is a view showing results of measuring a volumetric heat capacity C of the two
kinds of heat insulating films. The thermal conductivity λ and the volumetric heat
capacity C were calculated based on the following equations after measuring a specific
heat capacity Cp and a thermal diffusivity α with respect to two kinds of samples
(a sample containing hollow silica particles and a sample that did not contain hollow
silica particles).

[0039] Where, Cp represents specific heat capacity, ρ represents density, and α represents
thermal diffusivity.
[0040] The sample containing hollow silica particles (hereunder, referred to as "sample
A") was prepared as follows. First, a base material (test piece of aluminum alloy)
was subjected to an anodic oxidation treatment to form an anodic oxidation coating
film. Next, hollow silica particles (hollow silica particles manufactured by GRANDEX
Co., Ltd (primary particle diameter 90 to 110 nm)) were mixed in a polysilazane solution
(ingredients and percentages: diethyl ether 72%, poly(perhydrosilazane) 20%, and anisole
8%) and stirred adequately using a stirrer to thereby prepare a sealing material.
Thereafter, the sealing material was applied five times onto the anodic oxidation
coating film using a brush, and then dried and baked for 8 hours in a constant temperature
oven at 180°C to thereby prepare the sample A. The sample that did not contain the
hollow silica particles (hereunder, referred to as "sample B") was prepared in the
same manner as the sample A except that the polysilazane solution was used as the
sealing material.
[0041] The measurement conditions and the like for the specific heat capacity Cp and the
thermal diffusivity α were as follows.
(1) Specific heat capacity Cp
[0042] Measurement method: DSC method
[0043] Measurement apparatus: DSC Q1000 manufactured by TA Instruments
[0044] Reference sample: Sapphire
[0045] Measurement atmosphere: N
2 atmosphere
[0046] Measurement sample: After processing each sample to Φ6 mm, the base material was
dissolved in hydrochloric acid to prepare samples that were constituted only by film
(2) Thermal diffusivity α
[0047] Measurement method: Laser flash method
[0048] Measurement apparatus: LFA 457 manufactured by NETZSCH
[0049] Temperature measurement method: Noncontact temperature measurement using InSb sensor
Surface treatment: Graphite spray
[0050] Measurement atmosphere: N
2 atmosphere
[0051] Calculation technique: Base material and film were measured in an integrated state,
and the thermal diffusivity of only the film was calculated by multilayer analysis
including pulse width correction and heat loss.
[0052] The measurement results in Fig. 9 and Fig. 10 are shown as percentages based on the
sample B as 100%. As shown in Fig. 9 and Fig. 10, the thermal conductivity λ of the
sample A (with particles) is low in comparison to the sample B (without particles),
and the volumetric heat capacity C of the sample A is also lower than the sample B.
These results indicate that the heat insulating property of the sample A is superior
to that of the sample B. The fact that the sample A includes hollow silica particles
and the air in the internal space of the hollow silica particles functions similarly
to the air inside the pores 10b may be mentioned as one of the reasons why the heat
insulating property of the sample A is superior to that of the sample B.
[0053] The fact that the surface roughness Ra of the sample A is small may be mentioned
as another reason why the sample A has an excellent heat insulating property. Fig.
11 is a view illustrating results of measuring the surface roughness Ra. The surface
roughness Ra was measured with respect to both the sample A and the sample B that
were prepared in the same manner as described above. However, with respect to the
sample A, three different kinds of samples were prepared using three kinds of sealing
materials that were prepared by changing the mixing ratio of the hollow silica particles.
The porosity (= volume of internal space of hollow silica particles/volume of sample
x 100) after drying and baking the three kinds of sealing materials was as follows.
Sample A1: 27.3% (porosity: low)
[0054] Sample A2: 46.3% (porosity: medium)
[0055] Sample A3: 57.7% (porosity: high)
[0056] The surface roughness Ra was measured in accordance with JIS B601 (2001). The measurement
results in Fig. 11 are shown as percentages based on the sample B as 100%. As shown
in Fig. 11, the surface roughness Ra of the samples A1 to A3 (with particles) was
less than that of the sample B (without particles). Further, the surface roughness
Ra of the sample A3 was less than that of the sample A1 and the sample A2. The fact
that the surface roughness Ra is small means that the surface of the relevant sample
is smooth and a heat transfer area is small. Accordingly, it was found that the heat
insulating property of the sample A is superior to that of the sample B. Further,
it was found that the heat insulating property of the sample A3 is superior to that
of the sample A1 and the sample A2.