JP6524382B2 - Composite of metal or ceramic and glass with glass layer containing air bubbles - Google Patents

Description

The present invention is to provide a composite excellent in heat insulation by forming a glass layer containing air bubbles.

  A multilayer glass, which is a typical example of a heat insulating layer, is marketed emphasizing that it is unitized by providing a vacuum layer, an intermediate layer filled with dry air or argon gas, etc., without condensation or the like.

  Patent Document 1 discloses a technique in which a glass having two thermal expansion coefficients different from each other is formed to form a layer for reducing the thermal expansion coefficient difference between two glass layers. There is no phenomenon of dispersion in the glass layer, and it is a joint of a limited range of the contact surface, and it has a low function as a layer for alleviating heat conduction, and there is little heat insulating effect on itself.

  Patent Document 2 includes an adhesive layer containing 1 to 10% by volume of air bubbles with respect to the entire volume, but the firing temperature for vitrifying the adhesive layer is as high as 1000 ° C. or higher, and the energy efficiency is poor. If the material is metal, oxidation proceeds rapidly and degassing from the glass surface is also frequent.

  Although patent document 3 is a function which maintains heat insulation by providing air bubbles by a polymer binder layer, it can be predicted that it will be compressed if a force such as load is applied, and a failure will be caused in the heat insulation function.

  Patent Document 4 discloses a technique in which at least one selected from a fiber structure, a resin foam and a particle is used as a core, and the film is sealed with a film under reduced pressure and used as a heat insulator. In terms of sorting the contents further, it seems that consumers will be bothered.

JP, 2009-1260005, A JP, 2016-113335, A JP 2001-279877 A JP, 2002-58604, A

The thermal conductivity of the composite in which the substrate is a metal or ceramic surface coated with glass is affected by the substrate, and in some cases there is a failure such as a burn.

  For example, when putting a hot thing into a straw container and drinking it, it is difficult to hot drink the container.

  Tea cups made of ceramics are provided with handles to reduce heat.

  In the case of double glazing, if the intermediate layer is thickened to enhance the heat insulation, convection occurs in the enclosed gas, and the heat insulation tends to plateau.

In view of the above problems, we have devised that the problem can be solved by a composite that can adjust the heat conduction by using a layer containing bubbles in glass.

The invention described in claim 1 is a composite of metal or crystalline ceramic and glass, wherein the glass has a low temperature glass layer having a softening point of 420 ° C. or more and 660 ° C. or less, and a softening point of 700 ° C. or more. It consists of two layers of a high temperature glass layer of 870 ° C. or less, one of the two glass layers is in contact with the surface of the metal or ceramic, and the other glass layer is in contact with the one glass layer Metal or crystalline ceramic and glass including a glass layer including bubbles of 5 vol% or more and 50 vol% or less in volume bubble ratio between the high temperature glass layer and the low temperature glass layer by melting the low temperature glass layer Invention of the complex of

The low temperature glass layer is, for example, a glass frit for glaze, a glass (soda lime glass), a so-called soft glass such as a glass for vehicle, a hard glass such as B ₂ O _3, Al ₂ O ₃ , MgO, Bi ₂ O ₃ etc. Examples thereof include heat-resistant glasses such as borosilicate glass and aluminosilicate glass which are added, increased or reduced in weight, or both and adjusted to the softening point in the same range.

  The high-temperature glass layer may be, for example, soda lime glass to which filler such as borosilicate glass, aluminosilicate glass, or alumina is added to raise the apparent softening point and lower the fluidity, and both are beads, balloons, flakes or rods By forming the particles in the shape of a loop, it is possible to manufacture a bonding layer that contains air bubbles.

  There are two advantages of mixing the filler, one is that the softening point of the glass does not change, but the fluidity is suppressed during heating, the apparent softening point is increased, and the second is the defoaming that leaves bubbles. It is effective at suppressing, and the softening point of the present invention refers to both the original softening point and the apparent softening point due to the addition of the filler.

As an example, FIG. 1 brings a low temperature glass layer into contact with the surface of a metal or ceramic as a base material, brings a high temperature glass layer into contact with the surface of the low temperature glass layer, and heats the softening point of the low temperature glass layer to 900 ° C. or less. Although the low-temperature glass layer melts first and is a schematic view in which the glass layer including the air bubbles is formed by confining the air contained in the high-temperature glass layer, this combination is not limited.

FIG. 2 is a state diagram in which the two glass layers are in contact with each other before heating in FIG.

FIG. 3 is a photomicrograph of the sample prepared in Example 1 (FIG. 1), which shows that the gas present between the particles and / or in the particles of the high temperature glass layer at the film forming stage melts the low temperature glass layer. This is a glass layer that wets the surface of the high-temperature glass layer and infiltrates (tilts and disperses) inward along the particles between particles, and contains air bubbles in which the gas is trapped. It is a layer that retains the heat insulation function.

  The bubble condition that produces the effect is derived as the volumetric bubble rate.

  The number of air bubbles in the glass layer containing air bubbles is innumerable, and the size is controlled by the particle diameter of the high temperature glass layer, heating temperature, etc., as long as the surface of both or one glass layer is not reached. It has a function to be easily deformed and to absorb and disperse force, and a heat conduction suppressing effect.

  The specific volume of the arbitrary sample piece of the sample is "A", and the specific volume of the crushed sample is smaller than the minimum bubble of the layer containing that bubble, "B". It derives from the case of the ratio C = (1−A / B) × 100.

  The invention described in claim 2 includes the glass layer in which the air bubbles are contained according to claim 1, wherein the particle shape of the high temperature glass layer is a bead, a balloon, a scaly or rod shape having a diameter of 5 mm or less. It is an invention of a complex metal or crystalline ceramic and a glass complex.

  The use of a high temperature glass layer with a plurality of types of diameter or long diameter and different softening point types enables the distribution control of the diameter of the cells to be finely controlled, and the inclination to the inside of the low temperature glass layer is preferably performed. The dispersion depth can also be adjusted and effective in terms of heat conduction.

  The invention described in claim 3 is the invention of an article provided with a metal or crystalline ceramic containing a glass layer containing a bubble according to claim 1 and a glass composite.

The crystalline ceramics according to claim 1 are, for example, alumina minerals, magnesia minerals, crystalline ceramics for structures such as steatite, forsterite, zircon, etc., NTC thermistors, zinc oxide varistors, PTC thermistors, titanium series Ceramics of composite oxides such as varistors, nitrides, carbides, etc. correspond to the present invention, but the present invention is not limited thereto.

Representative examples of the metal described in claim 1 include iron, nickel, copper, titanium or alloys of the above-mentioned metals, for example, SUS, 9/1 copper, white copper, αβ alloy of titanium alloy, aluminum-magnesium alloy, etc. But there is no limitation to these.

The glass layer containing bubbles of 5% by volume or more and 50% by volume or less is a low-temperature glass layer in contact with metal or ceramics in the state of FIG. 2 as an example. It is a new layer that is trapped and formed by melting of the low temperature glass layer by the gas existing between the particles or within the particles of the high temperature glass layer being heated when being heated, but this combination is limited It is not what you are doing.

The infiltration (gradient dispersion) used in the present invention means that the low temperature glass layer having a low softening point and high fluidity by heating as shown in FIG. 4 wets the high temperature glass layer having a high softening point and low fluidity. It is a phenomenon that is dispersed to the inside while creating a concentration gradient that reduces the concentration, wets the glass particles, and forms a new glass layer bonded and bonded, which is a phenomenon different from Patent Document 1 and conventional bonding.

Glass layers containing air bubbles formed by infiltration (tilted dispersion) of a low temperature glass layer are both familiar because they are glass, and no cracks occur due to deterioration over time, and dispersion or when stress due to heat is applied It can be softened while absorbing and can improve heat insulation while preventing cracks, and since the material is metal or ceramic and glass, it is easy to recycle.

  The heat insulation effect is enhanced by the effect of the contained air bubbles, and the heat conduction from the substrate to the glass layer can be varied by controlling the shape and the bubble rate of the high temperature glass layer.

  This is lower in equipment cost than the conventional insulation method using composite glass, and the manufacturing cost can also be reduced.

FIG. 1 is an example of an article having the structure of the present invention, and this shape and the combination of a substrate and two layers of glass are not limited.

An example of the glass layer cross-sectional schematic view which contains air bubbles An example of the contact condition of the two glass layers before heating in FIG. 1 Example 1 Photomicrograph of the layer containing the bubbles of No and 4 in Table 1 Relationship image of infiltration (tilted dispersion) depth and viscosity of low temperature glass layer Surface temperature measuring device schematic

Borosilicate glass and aluminosilicate glass, which are examples of high temperature glass layers, are resistant to thermal shock, and their softening points are as high as 700 ° C. or higher, and their thermal expansion coefficients at 50 ° C. to 350 ° C. are 2.8 × 10 ⁻⁶ as reference values. above, 7.4 × 10 -6 ^/ degrees Celsius or less, Pyrex glass (registered trademark) as a representative example, heat cups for electronic components e glass, there is s glass for aerospace, particle shape of the present invention, the diameter or It is necessary to form in the shape of a balloon, a rod, a scale or a bead having a major axis of 5 mm or less.

  Further, by adding a filler such as alumina, magnesia or crystalline silica to the soda lime glass by 2 wt% or more and 35 wt% or less, the softening point is further moved to the high temperature side to lower the fluidity, and the shape is also bead, balloon, flake or The rod-shaped particles can be used as a high temperature glass layer.

  If the amount of filler added is less than 2% by weight, the amount of defoaming is large, and if it exceeds 35% by weight, the flowability is greatly reduced and it becomes difficult to control the size of air bubbles and the like.

The low temperature glass layer includes lower glaze frit, upper glaze frit including base glaze, etc. The softening point is as low as 420 to 660 ° C, it is weak to thermal shock, and the thermal expansion coefficient is 8 × 10 ^-6 or more as a reference value, 3 × The softening point and the thermal expansion coefficient can be adjusted by increasing or decreasing 10 ^-5 / ° C. or less, such as, but not limited to, phosphoric acid, lime, alumina, soda, and soda lime glass and the like.

Also, in order to adjust the heat resistance glass such as borosilicate glass or aluminosilicate glass to the softening point equal to the low temperature glass layer, RO (MgO, CaO, BaO etc.), R ₂ O (Li ₂ O, Na ₂ O, K ₂₎ Thermal expansion coefficient is also included by increasing, decreasing or adding O, etc., R ₂ O ₃ (Al ₂ O _3, B ₂ O ₃ etc.), R ₂ O ₅ (P ₂ O ₅ , V ₂ O ₅ ), etc. Adjustments are possible but are not limited to these materials.

The thermal expansion coefficient of crystalline ceramics is, for example, in the range of 4 × 10 ⁻⁶ to 15 × 10 ⁻⁶ / Celsius, and for metals in the range of 10 × 10 ^{−6 to} 25 × 10 ⁻⁶ / Celsius, so two-layer glass The coefficient of thermal expansion needs to be selected or blended to be compatible with the substrate.

Example 1 is an adiabatic effect comparison sample in which the bubble rate and its effect can be observed later.

In the base material of Example 1 (Table 1), a low temperature glass layer having a softening point of 530 ° C. is brought into contact with two types of steel plates for ceramics and ceramics, and a high temperature glass having a softening point of 780 ° C. so as to contact the low temperature glass layer. Apply a layer of borosilicate glass paste.

It is then dried to evaporate the water.

Next, by heating above the softening point of the low-temperature glass layer at 900 ° C. or less, the low-temperature glass layer melts after degreasing, and infiltrates while wetting the particle surface along the particles of the high-temperature glass layer not yet melted ) To form a glass layer containing air bubbles.

Contact the aluminosilicate glass (softening point 820 ° C) of four high temperature glass layers (Table 2) with spray-painting or contour printing on the surface of ceramics (stearite), dry it, and contact softening point 510 ° C The low temperature glass layer of the borosilicate glass paste is brought into contact and dried, and then heating is performed at 900 ° C. or less to obtain a composite having a form different from that of Example 1.

The heat insulation relationship of the layer containing the bubble produced in Example 1 and Example 2 is described in Tables 1 and 2.

実施例１及び２の試料に熱湯（９８℃）を注ぎ、図５の無風２５℃下で表面温度の変化を測定した。尚測定には放射温度計を用いた。

Hot water (98 ° C.) was poured into the samples of Examples 1 and 2, and the change in surface temperature was measured under a windless 25 ° C. of FIG. A radiation thermometer was used for the measurement.

  The method of observing the volumetric bubble rate is to scratch some of the glass layers of Examples 1 and 2 with a cutter or the like, and then perform impact or bending to collect sample pieces, or polish the substrate side to remove them. Sample pieces were collected, and then the specific gravity was measured with a pycnometer and the value was taken as "A". In order to prevent mixing of metals and ceramics, it is preferable to carry out sample processing under a microscope or a magnifying glass or to carry out a chemical treatment.

  Next, the same sample piece is crushed to a size smaller than the bubbles observed in FIG. 3, and the specific gravity is similarly measured with a pycnometer to make the value "B".

  The measurement sample was produced as mentioned above, and the volume bubble rate C = (1-A / B) x100 was derived.

  From the above calculation, it was observed that the volume bubble rate is preferably 5% by volume or more and 50% by volume or less. The higher the bubble rate, the higher the heat insulation effect, but one cycle is 20 ° C → 200 ° C → 20 ° C, and the thermal shock strength after repeating this 5 times is inferior, so more than 50% by volume and 5% by volume I will skip the test results that fall below.

  The bubble generation environment seems to be maintained under reduced pressure or atmospheric pressure or both depending on the particle size, particle shape and heating temperature of the high-temperature glass layer used and the coating method of the low-temperature glass layer in contact. It becomes a problem.

  It is possible to disperse and absorb the energy applied from the outside and to improve the heat insulation and mechanical strength by the existence of innumerable bubbles.

1 Composite of metal or ceramic and glass provided with a glass layer containing bubbles 2 Substrate (metal or ceramic)
3 One glass layer 4 The other glass layer 5 Air bubble 6 Glass layer containing air bubble 7 Many air bubbles 8 Bubble generation condition by microphotograph 9 Radiation thermometer 10 Sample stand 11 Sample 12 Measurement point 13 Measurement box

Claims (3)

  A composite of metal or crystalline ceramic and glass, wherein the glass has a low temperature glass layer having a softening point of 420 ° C. or more and 660 ° C. or less, and a high temperature glass layer having a softening point of 700 ° C. or more and 870 ° C or less And one of the two glass layers is in contact with the surface of the metal or ceramic, and the other glass layer is in contact with the one glass layer, and the low-temperature glass layer is melted. A composite of metal or crystalline ceramic and glass including a glass layer including a bubble having a volume bubble rate of 5% by volume or more and 50% by volume or less between the high temperature glass layer and the low temperature glass layer.   The glass of metal or crystalline ceramic containing a glass layer containing bubbles according to claim 1, wherein the particle shape of the high temperature glass layer comprises beads, balloons, flakes or rods having a diameter of 5 mm or less or longer. Complex. An article comprising a composite of a metal or a crystalline ceramic and a glass comprising the glass layer containing a bubble according to claim 1.

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