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EP-4741358-A1 - METAL-GLASS COMPOSITE

EP4741358A1EP 4741358 A1EP4741358 A1EP 4741358A1EP-4741358-A1

Abstract

A metallic glass composite is provided by preparing a thermally-spraying glass powder having a thermal expansion coefficient corresponding to a metallic base, which is a thermally spraying target, and suppressing air bubbles trapped in a glassy substance to enhance strength such as impact resistance. The metallic glass composite includes a metallic base made of a body-centered cubic ferrous material, and a thermally-sprayed glass portion formed at a film thickness of 10 to 2,000 µm on the metallic base. A glass material forming the thermally-sprayed glass portion includes: a first ingredient group A consisting of SiO 2 of 35 to 70 mass%; a second ingredient group B consisting of B 2 O 3 of 9 to 15 mass%, Li 2 O of 5 to 9 mass% and Na 2 O of 4 to 10 mass%, which is 18 to 30 mass% in total; and a third ingredient group C consisting of BaO of 0 to 15 mass%, TiO 2 of 2 to 15 mass%, Al 2 O 3 of 0 to 8 mass%, and ZnO of 0 to 15 mass%, which is 10 to 30 mass% in total. A proportion of a main ingredient D including these ingredient groups A, B and C is 90 mass% or more.

Inventors

  • NAKASHIMA, MIKIO

Assignees

  • Nakashima Sangyo Co., Ltd.

Dates

Publication Date
20260513
Application Date
20240614

Claims (7)

  1. A metallic glass composite, comprising: a metallic base made of a body-centered cubic ferrous material; and a thermally-sprayed glass portion formed at a film thickness of 10 to 2,000 µm on the metallic base, wherein a glass material forming the thermally-sprayed glass portion includes: a first ingredient group A consisting of SiO 2 of 35 to 70 mass%; a second ingredient group B consisting of B 2 O 3 of 9 to 15 mass%, Li 2 O of 5 to 9 mass% and Na 2 O of 4 to 10 mass%, which is 18 to 30 mass% in total; and a third ingredient group C consisting of BaO of 0 to 15 mass%, TiO 2 of 2 to 15 mass%, Al 2 O 3 of 0 to 8 mass%, and ZnO of 0 to 15 mass%, which is 10 to 30 mass% in total, wherein a proportion of a main ingredient D including the first ingredient group A, the second ingredient group B, and the third ingredient group C is 90 mass% or more, wherein a value of a linear expansion coefficient of the glass material in a range of room temperature to 300 degrees C is 9 to 11 (×10 -6 /degrees C), and wherein an area ratio of air bubbles having a diameter of 1 µm or more in a cross section of the thermally-sprayed glass portion in a thickness direction is less than 40%.
  2. A metallic glass composite, comprising: a metallic base made of a body-centered cubic ferrous material; and a thermally-sprayed glass portion formed at a film thickness of 10 to 2,000 µm on the metallic base, wherein a glass material forming the thermally-sprayed glass portion includes: a first ingredient group A consisting of SiO 2 of 50 to 60 mass%; a second ingredient group B consisting of B 2 O 3 of 2 to 8 mass%, Li 2 O of 8 to 15 mass% and Na 2 O of 8 to 20 mass%, which is 25 to 35 mass% in total; and a third ingredient group C consisting of BaO of 3 to 12 mass%, TiO 2 of 4 to 15 mass%, Al 2 O 3 of 0 to 5 mass%, and ZnO of 0 to 5 mass%, which is 10 to 20 mass% in total, wherein a proportion of a main ingredient D including the first ingredient group A, the second ingredient group B, and the third ingredient group C is 90 mass% or more, wherein a value of a linear expansion coefficient of the glass material in a range of room temperature to 300 degrees C is 14 to 17 (×10 -6 /degrees C), and wherein an area ratio of air bubbles having a diameter of 1 µm or more in a cross section of the thermally-sprayed glass portion in a thickness direction is less than 40%.
  3. The metallic glass composite of Claim 1 or 2, wherein a difference between the linear expansion coefficient of the glass material and a linear expansion coefficient of the metallic base is 15% or less.
  4. The metallic glass composite of Claim 1 or 2, further comprising: a molten solidified portion formed in an interface between the metallic base and the thermally-sprayed glass portion in the cross-section, the molten solidified portion being formed when the thermally-sprayed glass portion is embedded in the metallic base, wherein the molten solidified portion has a thickness of 0.3 µm or more.
  5. The metallic glass composite of Claim 1 or 2, wherein, in the thermally-sprayed glass portion, the area ratio of the air bubbles having the diameter of 1 µm or more, which exist in a region of 30% or less of the thermally-sprayed glass portion in the thickness direction starting from the interface between the metallic base and the thermally-sprayed glass portion in the cross-section is 50% or less.
  6. The metallic glass composite of Claim 1 or 2, wherein the film thickness of the thermally-sprayed glass portion is in a range of 10 to 100 µm, and the area ratio of the air bubbles having the diameter of 1 µm or more in the cross section of the thermally-sprayed glass portion in the thickness direction is less than 10%.
  7. The metallic glass composite of Claim 1 or 2, wherein the glass material includes an auxiliary ingredient E in addition to the main ingredient D, and wherein the auxiliary ingredient E includes one or two or more ingredients selected from a group consisting of CaO, SrO, MgO, P 2 O 5 , K 2 O, V 2 O 5 , Cr 2 O 3 , MnO 2 , Fe 2 O 3 , Co 3 O 4 , NiO 2 , CuO, Y 2 O 3 , ZrO 2 , NB 2 O 2 , MoO 3 , SnO 2 , Sb 2 O 3 , WO 3 , PbO, Bi 2 O 3 , La 2 O 3 , CeO 2 , Pr 6 O 11 , Nd 2 O 3 , Sm 2 O 3 and Gd 2 O 3 .

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present disclosure relates to a metallic glass composite, and more particularly, to a metallic glass composite obtained by thermally spraying a granulated glassy substance on a surface of a metal so that the granulated glassy substance is firmly adhered to the surface. 2. Description of Related Art When forming a glassy film on a metallic base, thermal spraying is used. By using the thermal spraying rather than enameling, a glass substance may be more firmly deposited on the metallic base to form a film. Therefore, the thermal spraying may be suitably used for a product which requires durability. In a thermal spraying apparatus, a thermally-spraying material such as glass, ceramics, for example, and a carrier gas are mixed with each other. Plasma is generated by a separately-supplied gas and a high current to cause high heat, so that a thermally-spraying glass powder made of the granulated glassy substance is melted. Thereafter, the thermally-spraying glass powder thus melted is discharged from the thermal spraying apparatus toward a metallic base to be thermally sprayed (see Patent Documents 1 and 2, for example). The metallic base and the glassy substance of the thermally-spraying glass powder are different in thermal expansion coefficient (linear expansion coefficient) from each other. In terms of specific heat, the metallic base is rapidly cooled. The metallic base and the thermally-spraying glass powder are different from each other in terms of a volume shrinkage rate. Thus, the thermal expansion coefficient needs to be controlled. This makes it extremely difficult to apply the thermal spraying with respect to such different materials. The present inventors developed a thermally-spraying glass powder and a thermal spraying method disclosed in Patent Document 1, and a thermal spraying apparatus disclosed in Patent Document 2. The present inventors established thermal spraying to be firmly applied to different materials such as a metallic base and a glassy substance of the thermally-spraying glass powder and fabricated a metallic glass composite. As disclosed in Patent Document 1, a surface of the metallic base to be thermally sprayed is heated while being roughened by sandblasting, for example. Thereafter, the glassy substance derived from the thermally-spraying glass powder melted by the thermal spraying is applied to the surface, thereby forming a film thereon. It is considered that the glassy substance derived from the thermally-spraying glass powder permeates into the roughened surface of the metallic base to improve adhesion between the metallic base and the glassy substance. Document in Related Art Patent Document Patent Document 1: Japanese Laid-Open Patent Publication No. 2013-216977Patent Document 2: Japanese Laid-Open Patent Publication No. 2021-130841 SUMMARY OF THE INVENTION Further, the present inventors have repeatedly conducted intensive studies on the formation of the glassy substance on the surface of the metallic base by the thermal spraying. As a result, the present inventors have found that the thermal expansion coefficient of the thermally-spraying glass powder needs to be adjusted in consideration of differences between thermal expansion coefficients of various types of metallic bases. Further, the present inventors have found that air bubbles, which are inevitably generated when the thermally-spraying glass powder is melted by the thermal spraying and deposited on the metallic base, degrade impact resistance of the glassy substance of a finished metallic glass composite. The present disclosure was made to solve the above-mentioned matters, and the present disclosure provides a metallic glass composite obtained by integrating different materials such as a metallic base and a glassy substance of a thermally-spraying glass powder by thermal spraying, in which the thermally-spraying glass powder is fabricated to have a thermal expansion coefficient corresponding to the metallic base to be thermally sprayed, and the glassy substance formed on the metallic base after the thermal spraying are suppressed from including air bubbles to increase strength such as impact resistance. That is, a metallic glass composite according to an example embodiment includes: a metallic base made of a body-centered cubic ferrous material; and a thermally-sprayed glass portion formed at a film thickness of 10 to 2,000 micrometer (µm) on the metallic base, wherein a glass material forming the thermally-sprayed glass portion includes: a first ingredient group A consisting of SiO2 of 35 to 70 mass%; a second ingredient group B consisting of B2O3 of 9 to 15 mass%, Li2O of 5 to 9 mass% and Na2O of 4 to 10 mass%, which is 18 to 30 mass% in total; and a third ingredient group C consisting of BaO of 0 to 15 mass%, TiO2 of 2 to 15 mass%, Al2O3 of 0 to 8 mass%, and ZnO of 0 to 15 mass%, which is 10 to 30 mass% in total. A proportion of a main ingredient D inclu