CN103938144A - Jet plating film and metal component with covering film - Google Patents

Abstract

The present invention provides a jet plating film and a metal component with a covering film. The jet plating film has excellent texture and tonality presented by porcelain and can also simultaneously realize mechanical characteristics such as sealability and hardness of a base material. The jet plating film is formed through deposition on the metal base material by jet plating particles whose main component is metallic oxide, and is provided with a first jet plating layer at a zone adjacent to the base material and a second jet plating layer at a zone including the surface of the jet plating film, and the porosity of the surface of the second jet plating layer is higher than 5% and lower than 15 %.

Description

Sputtered films of bismuth and the hardware with overlay film

Technical field

The present invention relates to sputtered films of bismuth and the hardware with overlay film.More specifically, relate to the sputtered films of bismuth forming by spraying plating and the hardware with overlay film that possesses this sputtered films of bismuth on surface.

Background technology

Give new functional technology and be still applied to various fields so far by overlay film is set on block base material.By the melting such as combustion flame or electric energy and this melt granules is accelerated by the spraying plating powder of metal, pottery (representational is the oxide-based pottery of being made up of metal oxide), sintering metal (cermet) etc. as the sputtering process of one of dry overlay film (dry coating) technology, the surface of block base material is blowed and sprayed and make its deposition, thereby form the gimmick of overlay film.

Wherein, utilize the spraying plating technology of ceramic powder of plasma spraying method etc. owing to can speciality both economical and that give stupalith with the form of thick film to base material being at high speed the chemical machinery characteristic that thermotolerance, wear resistant, erosion resistance and resistance to insulativity etc. are excellent like this, be therefore widely used in jet engine, gas turbine engine, processed for paper roller, pump shaft etc. towards the metal member of general industry.In addition, in recent years, this ceramic spray coating technology is also applied to the metal member of the equipment using in medical semiconductor applications etc., and above-mentioned additional function can be achieved more accurately.

Functional it has been generally acknowledged that by the following method of ceramic spray plated film is improved: improve the bonding force between melt granules and between base material and melt granules and suppress porosity compared with low and realize fine and close overlay film.And, think that this sputtered films of bismuth is to make the complete melting of spraying plating powder by (1), eliminate not melt granules, (2) make the melt granules of flight have large acceleration and with strong Impact energy, the surface of base material be clashed into and realize (for example,, with reference to patent documentation 1).

prior art document

patent documentation

Patent documentation 1: No. 2007/023976 specification sheets of International Publication

Summary of the invention

the problem that invention will solve

But, utilize the above-mentioned ceramic spray plated film of plasma spraying method to be only used as so far general industry purposes., practical situation are completely as the coating overlay film towards the electric product of ordinary consumer etc.This be because, the function requiring towards the coating overlay film of the electric product of ordinary consumer etc. is up to now mainly aesthetic appearance and adaptation, and the effect that representational coated film or the coated film being formed by the matrix material of resin and inorganic or metallic substance etc. that is coated film, metal-plated overlay film etc. by being formed by organic materialss such as various resins are formed by metallic substance realizes is met.

On the other hand, for example, in electric product towards ordinary consumer etc., from reasons such as the taking into account of miniaturization and and high strength, cost degradations, require outer exterior material to be covered by higher, the thinner coating overlay film of mechanical characteristics.For example, need to cover by light weight and there is thermal diffusivity but thin plate that the slightly poor aluminium alloy of mechanical characteristics is made with the high protective membrane of physical strength.In addition, about the coating overlay film of the machine to towards ordinary consumer etc., i.e. coating overlay film in commercial use, also expect to realize potentially the new aesthetic appearance of the vision of appealing to people.

But present situation is to provide diversified film although wrap resiniferous coated film, their thermotolerance and physical strength inequality.Although the overlay film physical strength being formed by metallic substance is than more excellent, aesthetic appearance is defined to (metallic color) outward appearance of metal, for example, can not corresponding want the requirement of naturally being felt such.In addition, about above-mentioned ceramic spray plated film, do not provide functional technology of this side of any raising aesthetic appearance.

Especially, for example in the case of using the thin plate of aluminium alloy as substrate applications in above-mentioned plasma spraying method, because the physical strength of base material becomes lower, therefore exist because knock (peening) that cause because of the shock of spraying plating particle produces the problem of being out of shape in base material self.In addition, the difference of the thermal expansivity in the sputtered films of bismuth being formed by pottery and the base material of aluminium alloy is large, therefore can notify to cause and in base material, produce the such problem of warpage because of the heat affecting in spraying plating.It should be noted that, although the depression of this less desirable base material, being created in ceramic spray coating technology in the past of warpage are the levels that is not considered as problem, during from this side of aesthetic appearance, may become great problem., this is for example delicate luminous reflectance degree exerted an influence or in the time grinding this sputtered films of bismuth, damage the worry of grinding energy because of existing.

The present invention makes in view of this aspect, and its object is to provide the brand-new ceramic spray plated film that has aesthetic appearance and mechanical characteristics concurrently.In addition, another object of the present invention is to provide the hardware with overlay film that possesses this sputtered films of bismuth.

for the scheme of dealing with problems

To achieve these goals, be that spraying plating particle taking metal oxide as main component deposits the sputtered films of bismuth forming on metal base by sputtered films of bismuth provided by the invention.And this sputtered films of bismuth possesses the 1st deposited metal in the region adjacent with above-mentioned metal base, possesses the 2nd deposited metal in the surperficial region that comprises above-mentioned sputtered films of bismuth.And, it is characterized in that, the surperficial porosity of above-mentioned the 2nd deposited metal is more than 5% and below 15%.

, sputtered films of bismuth of the present invention as above is made up of metal oxide in essence, does not comprise organic materials, the metallic substance such as such as resin.Therefore, artificial (plastics) texture ice-cold, that resin has having from metal products is completely different, can build distinctive natural sensation (texture) and feel (sense of touch) in such as ceramic ware etc.In addition, on this basis, can also obtain having concurrently the ceramic excellent chemical property having and the product of mechanical characteristics.

Such aesthetic appearance and chemical machinery characteristic can realize by the characteristic originally having from the metal oxide that forms sputtered films of bismuth, and can realize attractive appearance by above-mentioned specific the 2nd deposited metal.Particularly, the 2nd deposited metal is grinding surperficial in the situation that, can be configured to the deposited metal that can realize the beautiful outward appearance that has been endowed unique reflecting feel with the degree of depth.Such sputtered films of bismuth is that have never been realized so far, brand-new coating overlay film, is provided first by the present invention.

It should be noted that, in this specification sheets, " main component " refers to the meaning that comprises this composition with ratios more than 97 quality % in composition, representational refer to comprise 99 quality % above, be preferably that 99.5 quality % are above, this composition of 99.7 quality % above (for example,, more than 99.9 quality %) more preferably.

In addition, in a preferred embodiment of sputtered films of bismuth disclosed herein, be characterised in that, the porosity in the cross section vertical with substrate surface of above-mentioned the 1st deposited metal is more than 2% and below 20%.

By the 1st deposited metal of above-mentioned specific modality, mainly can suppress the impact to substrate and realize high closing force (overlay film adaptation).Particularly, the flexibility to base material and adaptation when the 1st deposited metal can be realized spraying plating, and realize the sputtered films of bismuth of mechanical properties excellence.

In a preferred embodiment of sputtered films of bismuth disclosed herein, be characterised in that, the median size of the spraying plating particle exposing on above-mentioned surface of above-mentioned the 2nd deposited metal is more than 1 μ m and below 30 μ m.

According to this formation, the surface of sputtered films of bismuth is formed by the spraying plating particle with median size as above, and the sputtered films of bismuth that has more improved the such aesthetic appearance of distinctive natural sensation in ceramic ware etc., feel can be provided.

In a preferred embodiment of sputtered films of bismuth disclosed herein, be characterised in that, the average pore diameter in above-mentioned the 1st cross section vertical with surface above-mentioned metal base deposited metal is more than 1 μ m and below 15 μ m.

The size that is above-mentioned scope by the hole making in the 1st deposited metal, can realize the physical strength of sputtered films of bismuth is improved more.

In a preferred embodiment of sputtered films of bismuth disclosed herein, be characterised in that, the average pore diameter in above-mentioned the 2nd cross section parallel with surface above-mentioned metal base deposited metal is more than 1 μ m and below 20 μ m.

By making the size that the hole of the 2nd deposited metal is above-mentioned scope, can realize higher aesthetic appearance.For example, in the time grinding this sputtered films of bismuth, can realize and be not only tone, even reflecting feel, light all have the coating overlay film degree of depth, extremely beautiful.

In a preferred embodiment of sputtered films of bismuth disclosed herein, be characterised in that, the thickness of above-mentioned the 1st deposited metal is more than 20 μ m and below 400 μ m.

The thickness of the 1st deposited metal is thinner more can seek lightweight, but excessive thinning can not fully obtain overlay film adaptation and mechanical characteristics.Therefore,, by making the thickness of the 1st deposited metal in above-mentioned scope, can realize the thinner of gauge control and guarantee the sputtered films of bismuth of adaptation and mechanical characteristics.

In a preferred embodiment of sputtered films of bismuth disclosed herein, be characterised in that, the thickness of above-mentioned the 2nd deposited metal is more than 10 μ m and below 400 μ m.

The thickness of the 2nd deposited metal is thinner more can seek lightweight, but because the optical transmission of the 1st deposited metal is high, in order not appear metal base, the 2nd deposited metal needs appropriate thickness.In addition, in the surperficial embodiment of grinding sputtered films of bismuth described later, preferably consider in advance by grinding the thickness of removing and form the 2nd deposited metal.From this viewpoint, by adjust the 2nd deposited metal in above-mentioned scope, can realize easily the thinner of gauge control and not affect the high sputtered films of bismuth of aesthetic appearance of the color of base material.

In a preferred embodiment of sputtered films of bismuth disclosed herein, be characterised in that, grind on the surface of above-mentioned the 2nd deposited metal.

By grinding the surface of above-mentioned the 2nd deposited metal, the excellent aesthetic appearance of sputtered films of bismuth of the present invention becomes more remarkable, so preferably.That is, for the sputtered films of bismuth that has carried out the form of grinding for surface, it feels gentle and emits light by light irradiation, therefore can realize with just like the extremely beautiful outward appearance that the porcelain of artistic products is equal to mutually.Or, can realization and natural stone, be known as the grand beauty that so-called jewel, pyroxene etc. are equal to for the mineral facies of appreciating and decorating.More specifically, for example, when metal oxide is aluminum oxide, can becomes almost completely pure white and emit unique outward appearance bright, as ceramic whiteware device by the irradiation of light.It should be noted that therefore the intrinsic propesties of the spraying plating particle of the 1st deposited metal based on being formed by metal oxide and be transparent thinks that this aesthetic appearance is mainly to realize by the formation of the 2nd deposited metal.In addition, for example, for ceramic whiteware device, in the surface coverage of that formed by kaolin, pure white and hard blank transparent and have glossiness vitreous glaze aspect completely different from forming of sputtered films of bismuth of the present invention.Therefore,, by this formation, provide extremely beautiful, the brand-new coating overlay film of tone (for example, white) with the degree of depth and reflecting feel.

In a preferred embodiment of sputtered films of bismuth disclosed herein, be characterised in that, the surface roughness Ra of above-mentioned the 2nd deposited metal is below 100nm.

Above-mentioned the 2nd deposited metal, by comprise the overlay film tissue of distinctive hole in sputtered films of bismuth, also can form the concavo-convex of appropriateness even if grind.Think concavo-convex by suitably forming this, the light reflective of realizing excellent gloss as above is improved.For example can realize taking Grossmeters as more than 75 excellent lights.In addition simultaneously, by this concavo-convex existence, sense of touch, feel in the time that people contacts this sputtered films of bismuth improve, and then also can realize appropriate skidproof effect.

In a preferred embodiment of sputtered films of bismuth disclosed herein, be characterised in that, above-mentioned metal oxide is aluminum oxide (alumina).

Above-mentioned sputtered films of bismuth can carry out all adjustment to its tone (form and aspect) by the composition of the metal oxide of this sputtered films of bismuth of formation.And especially in the time that above-mentioned metal oxide is aluminum oxide, for example, can realize almost complete hololeucocratic sputtered films of bismuth.In other words, can as ceramic whiteware, realize pure white and texture that have fine-textured skin aspect be more preferably.

In a preferred embodiment of sputtered films of bismuth disclosed herein, be characterised in that, in above-mentioned the 1st deposited metal, by in the X-ray diffraction analysis of the 1st deposited metal, from the diffracted intensity of (113) face of Alpha-alumina be made as I α, while being made as I γ from the diffracted intensity of (400) face of gama-alumina, by following formula (1):

Pα1（%）=Iα/（Iα+Iγ）×100···（1）

Defined Alpha-alumina one after another P α 1 is more than 8% and below 25%.

Not fully melting of spraying plating powder when the Alpha-alumina being comprised in the spraying plating particle that is main component with aluminum oxide can represent spraying plating mutually.The 1st deposited metal of this formation is so that the state of the melt granules of Alpha-alumina while having adjusted spraying plating in the residual mode of above-mentioned ratio.Under the impact energy that, the melt granules in the time more suitably having suppressed to clash into base material has and hot state, form sputtered films of bismuth.Therefore, sputtered films of bismuth of the present invention can be used as and further reduced the sputtered films of bismuth of the worry that produces depression, warpage in base material and provide.

In a preferred embodiment of sputtered films of bismuth disclosed herein, be characterised in that, in above-mentioned the 2nd deposited metal, by in the X-ray diffraction analysis of the 2nd deposited metal, from the diffracted intensity of (113) face of Alpha-alumina be made as I α, while being made as I γ from the diffracted intensity of (400) face of gama-alumina, by following formula (2):

Pα2（%）=Iα/（Iα+Iγ）×100···（2）

Defined Alpha-alumina one after another P α 2 is below 7%.

The 2nd deposited metal of this formation is so that the state of the melt granules of the mode that the residual quantity of Alpha-alumina phase is above-mentioned ratio while having adjusted spraying plating., most of melting of the melt granules while clashing into base material, forms sputtered films of bismuth under the state more improving in spraying plating particle adaptation each other.Therefore the plated film that the spraying plating particle that, sputtered films of bismuth of the present invention can be formed as comprising surperficial region adaptation is each other improved.

In addition, in other side, be characterised in that according to the hardware with overlay film provided by the invention, possess any above-mentioned sputtered films of bismuth on the surface of metal base.

Known, if being carried out to direct spraying plating, the metal base of iron and steel etc. forms the sputtered films of bismuth of being made by metal oxides such as aluminum oxide in the past, cannot obtain sufficient closing force.Therefore, in order to improve this closing force, the stratum basale that formed by metal is set between the sputtered films of bismuth conventionally forming at metal base with by metal oxide, this be indispensable (for example,, with reference to patent documentation 1).But, be for example the spraying plating particle that for example flat and particle diameter is larger by the particle that makes to form the 1st deposited metal, can adaptation form well above-mentioned sputtered films of bismuth, it is hereby ensured the adaptation requiring in the purposes of for example business.

Thus, can provide and possess the also hardware of the sputtered films of bismuth of excellent pottery of aesthetic appearance on the basis of adaptation and mechanical characteristics.For example, can provide to build the metallicity member of the feel having fine-textured skin and then possess as ceramic ware and have the hardware color and luster of the degree of depth, that there is extremely beautiful outward appearance.

In a preferred embodiment of the hardware with overlay film disclosed herein, be characterised in that, above-mentioned metal base is aluminium or its alloy.

Aluminium and its alloy are light weights among metallic substance, excellent thermal conductivity, therefore Recent study as the use of the outer exterior material of the electric product such as PC, mobile telephone etc.But also there is on the other hand such shortcoming that easily sustains damage in aluminium or its alloy.For example, but the physical strength excellence of above-mentioned sputtered films of bismuth, can be high rigidity.Therefore, the member being formed by aluminium or its alloy by employing, as the base material of the hardware with overlay film of the present invention, can be given excellent physical strength to the base material of this aluminium system, can more effectively bring into play advantage of the present invention, so preferably.

In a preferred embodiment of the hardware with overlay film disclosed herein, be characterised in that, the thickness of above-mentioned metal base is below 5mm.

Above-mentioned sputtered films of bismuth can be to have reduced as the state of the Impact energy of the metal oxide particle of spraying plating raw material and the temperature of the melt granules of this metal oxide is suppressed for low state, the surface of metal base to be clashed into, thus formation.Therefore, even during as base material, also can obtain aptly not making with the hardware of overlay film base material distortion at the thinner metal sheet of used thickness.Especially, even in the time making thickness and be the base material of aluminium below 5mm system, also can obtain aptly the hardware with overlay film.

In a preferred embodiment of the hardware with overlay film disclosed herein, be characterised in that, above-mentioned metal base has carried out surface roughening, and above-mentioned metal base and above-mentioned sputtered films of bismuth are by physical construction and integrated.

To having carried out in advance the metal base of surface roughening, utilize spraying plating to form above-mentioned sputtered films of bismuth, can obtain thus the hardware with overlay film that the adaptation of metal base and sputtered films of bismuth fully improves.For example, can obtain sputtered films of bismuth is hardware more than 5MPa to the dhering strength of metal base.The hardware with overlay film that any one that thus, can realize aesthetic appearance, mechanical characteristics and film adaptation all realizes with high level.

As mentioned above, being possessed the sputtered films of bismuth being formed by metal oxide (so-called oxide-based pottery) by the hardware with overlay film provided by the invention, can be therefore the hardware of the chemical machinery excellent that thermotolerance, wear resistant, erosion resistance and resistance to insulativity etc. and so on are excellent in essence.On this basis, also realized and possessed excellent aesthetic appearance by the hardware with overlay film provided by the invention.Therefore, can be preferably used as the member of the various article of commercial use.For example, can be as the article that general human consumer provided, require attractive appearance and hobby property, the outer exterior materials of for example article taking residential equipments such as the building materials such as life groceries, panel, various power generation systems such as various electric products, cooking apparatuss as representative etc. etc. use aptly.Especially, can be preferably used as the outer exterior material requiring as the electric product of the character such as high strength, thermal diffusivity and the insulativity of outer exterior material.As this electric product, can exemplify mobile telephone, PC and peripheral equipment thereof, TV as one example, blue ray recorder, AVC equipment, the stereo equipments such as camera, AV equipment, the refrigerators such as automobile navigation, air-conditioning, the beauty health-care equipment such as the life electric installations such as air cleaning machine, blower etc.

Brief description of the drawings

Fig. 1 is the sectional view that schematically shows the formation of the hardware with overlay film of an embodiment.

Fig. 2 is the sectional view that schematically shows the formation of the hardware with overlay film of other embodiment.

description of reference numerals

1 sputtered films of bismuth

10 the 1st deposited metals

12 spraying plating particles

14 holes

20 the 2nd deposited metals

22 spraying plating particles

24 holes

30 metal bases

The hardware of 100,100a with overlay film

Embodiment

Below, with reference to suitable accompanying drawing, the embodiment based on suitable is to sputtered films of bismuth of the present invention and describe with the hardware of overlay film.It should be noted that, for example, hold as customary means prior art, those skilled in the art the item mentioning especially in this specification sheets (feature of sputtered films of bismuth etc.) item in addition, that the necessary thing of enforcement of the present invention (, using method of the formation of coating apparatus, this coating apparatus etc.) can be used as based on this field.The present invention can the technology general knowledge based in disclosed content in this specification sheets and this field implement.In addition, the relation of size in each figure (length, width, thickness etc.) roughly represents the feature of the form of sputtered films of bismuth of the present invention and the hardware with overlay film, might not reflect the size relationship in actual sputtered films of bismuth and the hardware with overlay film.

［ formation of the hardware with overlay film ］

Fig. 1 is the sectional view that schematically shows the formation of the hardware with overlay film of an embodiment.Hardware with overlay film 100 disclosed herein for example as shown in Figure 1, possesses sputtered films of bismuth 1 on the surface of metal base 30.

As the material that forms metal base 30, have no particular limits, can use various metallic substance.For example can exemplify the refractory alloy taking various SUS materials etc. as the iron and steel of representative, taking inconel (Inconel) etc. as representative, low expansion alloy taking Invar alloy (Invar), Kovar alloy (Kovar) etc. as representative, corrosion resisting alloy taking haas troy alloy (Hastelloy) etc. as representative, taking aluminium alloy as 1000 useful series～7000 series alloys such as lightweight construction material etc. as representative etc.Impact when melt granules when sputtered films of bismuth 1 of the present invention can reduce spraying plating clashes into metal base 30 forms with heat.Therefore,, in the time using aluminum or aluminum alloy as metal base 30, especially, in the case of using the thin plate of aluminium alloy, the speciality of the hardware 1 with overlay film of the present invention becomes obviously, so particularly preferably.The thin plate of this aluminium alloy can be for example that thickness is below 5mm, below for example 3mm, further can be defined as below 1mm.Below, the situation taking the thin plate that uses aluminium alloy as metal base 30 describes as example.

Though Fig. 1 is not shown, metal base 30 also can make to possess by chemical gimmicks such as physics gimmick, etching such as such as sandblast processing the surface roughening of sputtered films of bismuth 1., also can be provided with on the surface of metal base 30 small concavo-convex.By destroying so in advance the surface of metal base 30, sputtered films of bismuth 1 enters into the surperficial concavo-convex of metal base 30, and metal base 30 and sputtered films of bismuth 1 are by mortise mechanically.The configuration of surface realizing by this roughened etc. is had no particular limits, and the surface roughness Ra of the metal base 30 of for example can example sening as an envoy to is 0.2 μ m～20 μ m left and right.

And this sputtered films of bismuth 1 consists of the spraying plating particle 12,22 of deposition taking metal oxide as main component on the metal base 30 above-mentioned.More specifically, this sputtered films of bismuth 1 possesses the 1st deposited metal 10 in the region adjacent with metal base 30, in addition, possesses the 2nd deposited metal 20 in the surperficial region that comprises sputtered films of bismuth 1.In present embodiment, exemplify the situation of the double-deck sputtered films of bismuth 1 being formed by the 1st deposited metal 10 and the 2nd deposited metal 20.It should be noted that, as long as possess the 1st deposited metal 10 in the region adjacent with metal base 1, possess the 2nd deposited metal 20 in the surperficial region that comprises sputtered films of bismuth 1, also can between the 1st deposited metal 10 and the 2nd deposited metal 20, possess the deposited metal of other form.

Herein, as the metal oxide that forms spraying plating particle 12,22, there is no particular limitation, can be made as the oxide compound of various metals.As the metallic element that forms this metal oxide, for example, can list and be selected from B, Si, Ge, Sb, the metalloid elements such as Bi, Mg, Ca, Sr, Ba, Zn, Al, Ga, In, Sn, the typical elements such as Pb, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu, Ag, the transition metals such as Au, La, Ce, Pr, Nd, Er, one kind or two or more in the lanthanon such as Lu.Be particularly preferably and be selected from Mg, Y, Ti, Zr, Cr, Mn, Fe, Zn, Al, the one kind or two or more element in Er.

More specifically, as metal oxide, for example, can list MgO, CaO, SrO, Sc ₂o ₃, Y ₂o ₃, La ₂o ₃, TiO ₂, ZrO ₂, HfO ₂, VO _x(for example V ₂o ₅deng), Nb ₂o ₃, Ta ₂o ₅, CrO _x(for example Cr ₂o ₄deng), WO _x(for example WO ₂, WO ₃deng), MnO _x(for example MnO, MnO ₂, Mn ₃o ₄deng), FeO _x, CoO _x, NiO, CuO, AgO, ZnO, Al ₂o ₃, MgAl ₂o ₄, Al ₆o ₁₃si ₂, Ga ₂o ₃, In ₂o ₃, SnO ₂, BiO _x, CeO ₂, PrO _x, Nd ₂o ₃, Er ₂o ₃, Lu ₂o ₃, ZrSiO _x, ZrAlO _x, HfSiO _x, HfAlO _x, TiSi _xo _y, B ₂o ₃, SiO ₂, GeO ₂, Sb ₂o ₅deng.

The composition of this metal oxide can be considered to give the desired characteristic of sputtered films of bismuth 1 and suitably determine.This characteristic can refer to the aesthetic appearance such as the chemical propertys such as physical property, fusing point, chemical proofing, pattern, tone such as the such as mechanical characteristics such as hardness, toughness, specific refractory power, thermal conductivity, specific conductivity etc.Above-mentioned metal oxide both can a kind forms separately spraying plating particle 12,22, also can combine in addition two or more and form spraying plating particle 12,22.For example, in the situation that spraying plating particle 12,22 comprises two or more metal oxide, part or all of these oxide compounds also can form composite oxides.And then, for above-mentioned metal oxide, for example for adjust sputtered films of bismuth 1 tone object, as from the material of used raw material (natural matter) etc., also can comprise the element (for example, Na, K, Rb etc.) beyond above-mentioned example.In addition, the element that forms above-mentioned oxide compound also can be with the form of ion etc. and is involved.

Below, as a suitable embodiment of sputtered films of bismuth disclosed herein, taking metal oxide as aluminum oxide (Al ₂o ₃) situation be example, the feature of sputtered films of bismuth of the present invention is elaborated.

The 1st deposited metal 10, as seen in common sputtered films of bismuth, is mainly deposited and is formed by flat spraying plating particle 12.In addition, the 2nd deposited metal 20, as seen in common sputtered films of bismuth, is mainly deposited and is formed by flat spraying plating particle 22.And, can form hole 14,24 at the periphery of this spraying plating particle 12,22.

Herein, the porosity in the cross section vertical with base material 30 surfaces of the 1st deposited metal 10 is preferably more than 2% and below 20%.

The existence of the hole 14,24 in sputtered films of bismuth 1 can produce considerable influence to the mechanical characteristics of overlay film 1 and adaptation.In sputtered films of bismuth 1 of the present invention, be below 20% by the porosity in the cross section vertical surface with base material 30 of the 1st deposited metal 10 is suppressed, thereby suppress the warpage of the base material 30 being caused by the 1st deposited metal 10 and the difference of the thermal expansivity of base material 30, and guarantee the high adhesion to base material 30.In order to suppress the warpage of base material 30, preferably the porosity of the 1st deposited metal 10 is made as more than 2%, and representational is more than 5%, for example, can be made as more than 10%.But, when porosity is too high, there is the worry of adaptation reduction or overlay film lower hardness, so not preferred.From this aspect, the porosity of the 1st deposited metal 10 is made as below 20%.Porosity is representational is below 18%, for example, can be below 15%.

Herein, be to carry out by the observation image of the section structure substantially vertical with base material 30 to sputtered films of bismuth 1 value that image analysis is obtained about the porosity of the 1st deposited metal 10.Particularly, cut out the cross section arbitrarily of the thickness direction of the hardware 100 with overlay film, and with regulation multiplying power this cross section of microscopic examination in sputtered films of bismuth 1(for example, the 1st deposited metal 10) tissue, to the observation image obtaining therefrom carry out by hole portion and solid phase part from 2 values, and use image analysis software to analyze it, can measure thus porosity.It should be noted that, in this manual, the mensuration of porosity is carried out as follows: according to based on scanning electron microscope (SEM; Hitachi High-Technologies Corporation. manufactures, S-3000N) observation image (can be suitably any one of secondary electron image, composograph or radioscopic image.), use image analysis software (NIPPON ROPER K.K. manufacture, Image-Pro Plus) to carry out image analysis.

It should be noted that, the form of the hole 14,24 comprising in sputtered films of bismuth 1 depends on the sedimentation state of spraying plating particle 12,22, and therefore in the direction of the direction vertical with respect to base material 30 and level, its situation is different sometimes.On the cross section vertical with base material 30, evaluating is the opinions based on following about the porosity of the 1st deposited metal 10: the porosity of being evaluated by this cross section affects adaptation and the heat shrinkability characteristic of the 1st deposited metal 10 more.

When in the 1st deposited metal 10, contained hole 14 includes macrovoid on a small quantity, the intensity of the 1st deposited metal 10 is because of the local reduction of this hole 14, so not preferred.Therefore more than, in the 1st deposited metal 10, the average pore diameter of contained hole 14 is preferably 1 μ m and below 15 μ m.

In this specification sheets, refer to that about the average pore diameter of the 1st deposited metal 10 direction of the regulation to the hole 14 in the cross section vertical with the surface of base material 30 measures the mean value of the diameter of gained (determining orientation average diameter).This average pore diameter and above-mentioned porosity similarly the observation image of the section structure to 1st deposited metal 10 substantially vertical with base material 30 are carried out image analysis and are obtained.For example, carried out the hole portion of 2 values about the observation image to preparation described above, the size of the hole part of the direction of mensuration regulation also averages, thereby can obtain.It should be noted that, in this specification sheets, the mensuration of average pore diameter and the mensuration of above-mentioned porosity are similarly carried out as follows: according to based on scanning electron microscope (SEM; Hitachi High-Technologies Corporation. manufactures, S-3000N) observation image (can be suitably any one of secondary electron image, composograph or radioscopic image.), use image analysis software (NIPPON ROPER K.K. manufacture, Image-Pro Plus) to carry out image analysis.

The 1st above deposited metal 10 is in order to suppress impact, the heat affecting of melt granules to metal base 30, can be the deposited metal that the central part condition spraying plating that melting is not such, Impact energy is lower forms with the circumference melting of spraying plating powder only.Meanwhile, because the state of the abundant melting of circumference with spraying plating powder deposits, therefore can guarantee adaptation and melt granules 12 adaptation each other of spraying plating particle 12 to metal base 30.For example, the 1st deposited metal 10 forming taking this condition spraying plating can form for example, extremely fine and close tissue as (, more than 2% and below 5%) more than 2% and below 20% of porosity aptly.

Herein, for the molten state of the spraying plating particle 12 in the 1st deposited metal 10, in the total of the part (hereinafter referred to as puddle) of the molten state of the part of the not molten state of melting not (hereinafter referred to as puddle not) and temporary transient melting, the shared ratio of puddle can not be suppressed to the ratio of regulation.

This not the shared ratio of puddle for example can analyze to hold by the observation image of the section structure vertical with base material 30 to the 1st deposited metal 10 by image analysis software.That is, obtain area and the area of puddle not of the puddle of the spraying plating particle 12 in the 1st deposited metal 10, can calculate the not shared ratio of puddle according to them.It should be noted that, the area of the puddle of spraying plating particle 12 for example can obtain as follows with the area of puddle not: observe with the tissue in the cross section vertical with base material 30 of the 1st deposited metal 10 with the microscope of regulation multiplying power pair, use image analysis software to carry out, by puddle and 2 values that puddle does not separate, calculating area separately to the observation image of gained thus.It should be noted that, for the spraying plating particle 12 of the 1st deposited metal 10, by puddle when puddle does not separate, when visual image, the part that the shape of not residual original spraying plating powder can be presented to flat shape is judged as puddle, and the part that the centre portions of residual original spraying plating powder has been maintained to the shape of particle is judged as not puddle.

The shared ratio of not puddle so operating and obtain is preferably roughly more than 1% and below 25%.

On the other hand, the molten state of this spraying plating particle 12 depends on the kind of metal oxide, but also can confirm according to the ratio of the crystalline phase that for example forms metal oxide.For example, the 1st deposited metal 10, can be confirmed by the ratio of the gama-alumina of the Alpha-alumina of high-temperature stable phase and low-temperature phase during as the constituent of spraying plating particle 12 for main component comprising aluminum oxide (alumina).That crystalline structure is the Alpha-alumina of hexagonal system as the normally used alumina particle of spraying plating powder, this alumina particle chilling after melting, thus Alpha-alumina changes the gama-alumina that (phase transformation) is isometric system.In the 1st deposited metal 10 Alpha-alumina with ratio as above exist be because:, can represent that spraying plating particle does not have complete melting, representational is near the meaning there to be the mutually residual state deposition of Alpha-alumina the heart therein.

In the 1st deposited metal 10, Alpha-alumina shared ratio in the total of Alpha-alumina phase and gama-alumina phase for example can be used as Alpha-alumina one after another (P α 1) and indirectly obtains as follows.; the value of P α 1 for trying to achieve as follows: the X-ray diffraction (XRD) carrying out the 1st deposited metal is analyzed; by the diffracted intensity of (113) face from Alpha-alumina be made as I α, while being made as I γ from the diffracted intensity of (400) face of gama-alumina, with P α 1(%)=I α/(I α+I γ) × 100 values of obtaining.It should be noted that, in this manual, X-ray diffraction analysis uses X-ray diffraction device (Rigaku Corporation manufacture, UltimaIV).

It should be noted that, for example, in the time that metal oxide is aluminum oxide, the shared ratio of Alpha-alumina (can be not fusing department) can be for example more than 8% situation using above-mentioned P α 1 as preferably, more preferably more than 10% left and right, more preferably more than 12% left and right.But the surplus ratio of Alpha-alumina (can be not melt rate) too much can cause the fully melting of spraying plating powder, so not preferred.From this aspect, the shared ratio of Alpha-alumina can be for example situation below 25% using above-mentioned P α 1 as preferably, more preferably below 20%, further suitable being made as below 18%.

It should be noted that, the metal oxide that forms spraying plating powder can be that crystallinity is high, material to visible transparent conventionally.Therefore, the 1st deposited metal 10 with above tissue is for example, with metal oxide particle (, alumina particle) characteristic originally same, and the transmissivity of visible ray is high and can be transparent., can cause larger crystal boundary, the hole 14 of the degree of scattering of light in 12 not a large amount of formation of spraying plating particle.And spraying plating particle 12 each other adaptation deposits admirably.Like this, for example, in order to make the not melting of central part (when the aluminum oxide, residual Alpha-alumina phase) of spraying plating powder, circumference melting ground, adaptation deposit spraying plating particle 12 admirably, and it is suitable for example using larger spraying plating powder.Because the tissue morphology of sputtered films of bismuth 1 is extremely complicated, be therefore difficult to shape and the size of specific spraying plating particle 12, for example representational, the 1st deposited metal 10 can deposit and form compared with large spraying plating particle 12 for particle diameter.The 1st deposited metal 10 like this can be for example the plasma spraying of the spraying plating powder below the above 40 μ m of 20 μ m and forming aptly by having used median size.Thus, can guarantee that metal base 30 is extensive with the contact area of spraying plating particle 12, realize the 1st deposited metal 10 that adaptation and film toughness etc. are excellent.

In addition, although be not particularly limited, more than the thickness of the 1st deposited metal 10 is preferably made as 20 μ m and below 400 μ m.The thickness of the 1st deposited metal 10 is thinner more can seek lightweight.Therefore, the thickness of the 1st deposited metal 10 is more preferably made as below 350 μ m, for example, can be made as below 300 μ m.But, if the thickness of the 1st deposited metal 10 became thin, cannot fully obtain overlay film adaptation and mechanical characteristics.Therefore, the thickness of the 1st deposited metal 10 be preferably made as 50 μ m above, for example can be made as 100 μ m more than.Thus, can realize the thinner of gauge control and guarantee the sputtered films of bismuth 1 of adaptation and mechanical characteristics.

On the other hand, be more than 5% and the 15% following feature of giving by making the surperficial porosity of the 2nd above-mentioned deposited metal 20.

The existence of the hole 14,24 in sputtered films of bismuth 1 can affect greatly the mechanical characteristics of overlay film 1 and adaptation.In sputtered films of bismuth 1 of the present invention, by the surperficial porosity of the 2nd deposited metal 20 is defined as to above-mentioned scope, thereby guarantee spraying plating particle 22 clinging power and the higher appearance of realization each other.In order to possess the aesthetic appearance of excellence as above in sputtered films of bismuth 1, the porosity of the 2nd deposited metal 20 must be made as more than 5%, is preferably typically more than 6%, for example can is more than 8%.But too high porosity can be damaged dhering strength, the overlay film intensity of the 2nd deposited metal 20.From this aspect, the porosity of the 2nd deposited metal 20 is made as below 15%.Porosity is preferably below 13%, for example can be below 11%.

In addition, be to carry out by the observation image of the surface structure to sputtered films of bismuth 1 value that image analysis is obtained about the porosity of the 2nd deposited metal 20.Particularly, with the tissue on surface (, the surface of the 2nd deposited metal 20) of the microscopic examination sputtered films of bismuth 1 of regulation multiplying power, to the observation image obtaining carry out by hole portion and solid phase part from 2 values, and use image analysis software to analyze it, can measure thus porosity.It should be noted that, in this manual, be also to carry out as follows to the mensuration of the porosity about the 2nd deposited metal 20: according to based on scanning electron microscope (SEM; Hitachi High-Technologies Corporation. manufactures, S-3000N) observation image (can be suitably any one of secondary electron image, composograph or radioscopic image.), use image analysis software (NIPPON ROPER K.K. manufacture, Image-Pro Plus) to carry out image analysis.

It should be noted that, it is the opinion based on following that the porosity about the 2nd deposited metal 20 is evaluated on its surface: the porosity of being evaluated by this surface can produce considerable influence to the aesthetic appearance of sputtered films of bismuth 1.

The median size of the spraying plating particle 22 that the 2nd deposited metal 20 more preferably exposes on the surface of sputtered films of bismuth 1 is more than 1 μ m and below 30 μ m.That is, the layer that the 2nd deposited metal 20 is the Porous that comprises hole 24, its configuration of surface can be for having appropriate concavo-convex form, and described appropriateness concavo-convex is that the particle of the median size by having above-mentioned scope forms.It should be noted that, spraying plating particle 22 is same with metal oxide particle, and the transmissivity of visible ray is high and can be transparent in essence, but light, on its surface, scattering occurs, and see base material thereby human eye can not see through it.

Therefore, by making the median size of spraying plating particle 22 and the porosity of the 2nd deposited metal 20 in above-mentioned scope, the 2nd deposited metal 20 presents and the corresponding color of composition and the scattering of light situation etc. of metal oxide, can become the natural sensation that possesses the blank etc. of ceramic ware and show, the form of feel by its configuration of surface.For example, in the time that metal oxide is aluminum oxide, the 2nd deposited metal 20 presents the white same with alumina powder, can possess that the blank of parian ware shows pure white and possess the feel having fine-textured skin.It can be above, for example more than 10 μ m that the median size of spraying plating particle 22 is preferably 5 μ m.In addition the median size of spraying plating particle 22 be preferably 25 μ m following, for example can be below 20 μ m.The 2nd deposited metal 20 like this can be for example that 1 μ m plasma spraying above and spraying plating powder below 20 μ m forms aptly by having used median size.

It should be noted that, median size refers to the particle diameter (50% volume average particle size) of the accumulated value 50% in the size-grade distribution of measuring by the particle size distribution device based on laser light scattering diffraction approach.In this manual, the mensuration of median size adopts the value that the laser diffraction/diffuse transmission type particle size measurement device " LA-300 " that uses Horiba Ltd to manufacture obtains.

It should be noted that, in this manual, the median size of the spraying plating particle 22 exposing on surface of sputtered films of bismuth 1 refers to the mean value (determining orientation average footpath) of the diameter of measuring in the direction of the regulation of being seen spraying plating particle 22 in the time observing sputtered films of bismuth 1 surperficial.For this median size, the tissue on the surface of the microscopic examination sputtered films of bismuth 1 of the multiplying power specifying by use (, the surface of the 2nd deposited metal 20) is also measured the observation image obtaining.In this specification sheets, the mensuration of the median size of the spraying plating particle 22 exposing on surface is carried out as follows: according to based on scanning electron microscope (SEM; Hitachi High-Technologies Corporation. manufactures, S-3000N) observation image (can be suitably any one of secondary electron image, composograph or radioscopic image.), use image analysis software (NIPPON ROPER K.K. manufacture, Image-Pro Plus) to carry out image analysis.It should be noted that, about 2 values, for example, can for example, for example, suitably implement by capping threshold value in above-mentioned image analysis software (130) and lower threshold (0).

But the sputtered films of bismuth of porous often becomes that spraying plating particle 22 combination is each other weak, the sputtered films of bismuth of mechanical properties.Therefore, in the 2nd deposited metal 20, preferably as the almost melting and depositing completely of the metal oxide particle of depositing materials.For example, in the time that metal oxide is aluminum oxide, as the shared ratio P α 2 of the Alpha-alumina in the 2nd deposited metal 20 (not fusing department), can similarly obtain with the situation of above-mentioned the 1st deposited metal 10.; P α 2 is following value: the X-ray diffraction (XRD) carrying out the 2nd deposited metal is analyzed; by the diffracted intensity of (113) face from Alpha-alumina be made as I α, while being made as I γ from the diffracted intensity of (400) face of gama-alumina, with P α 2(%)=I α/(I α+I γ) × 100 values of obtaining.And in the aluminum oxide as the constituent of spraying plating particle 22, Alpha-alumina shared ratio in the total of Alpha-alumina and gama-alumina, as P α 2, is preferably below 7%., as the almost melting and depositing completely of the alumina particle of depositing materials.Therefore, spraying plating particle 22 can with almost completely the state adaptation of melting be attached to well on the 1st deposited metal 10, and spraying plating particle 22 each other also adaptation mutually combine mutually well.The shared ratio of this Alpha-alumina (not fusing department), as P α 2, is preferably below 5%, more preferably below 3%.

And then for hole 24 contained in the 2nd deposited metal 20, while comprising excessive space, the intensity of the 2nd deposited metal 20 is local reduction due to this hole 24, so not preferred.More than the average pore diameter of the hole 24 that therefore, the 2nd deposited metal 20 comprises is preferably 1 μ m and below 20 μ m.

The average pore diameter of the 2nd deposited metal 20 can similarly be obtained with the situation of above-mentioned the 1st deposited metal 10.

In addition, though there is no particular limitation, as an embodiment, as preferred example, it is above and below 200 μ m that the thickness that can exemplify the 2nd deposited metal 20 is made as 10 μ m.Because the 1st deposited metal 10 is transparent, therefore in order to prevent that seeing through it sees metal base 30 and more than the thickness of the 2nd deposited metal 20 is made as to 10 μ m.This thickness is more preferably more than 20 μ m, for example, more than can being made as 50 μ m.But, if the 2nd deposited metal 20 is than the required thicker lightweight that is difficult to seek, therefore for example preferably thickness is made as below 200 μ m, be further made as below 150 μ m, for example can be made as below 100 μ m.Thus, can realize gauge control thinner and guaranteed the sputtered films of bismuth 1 of aesthetic appearance.

Fig. 2 is the grinding sectional view of the formation of the hardware 100a with overlay film on surface excessively that schematically shows an embodiment.As illustrated in this Fig. 2, it is also the suitable embodiment of sputtered films of bismuth 1 of the present invention and the hardware 100a with overlay film that the surface of the 2nd deposited metal 20 has carried out grinding.More preferably mirror ultrafinish of this grinding.If the surface to the 2nd deposited metal (, the surface of sputtered films of bismuth 1) grinds, be positioned at surperficial spraying plating particle 22 and partly pruned and expose abrasive surface.The spraying plating particle 22 grinding and unique effect that can show optics at the spraying plating particle 22 of its periphery existence are carried out herein.

That is, light does not reflect on the surface of spraying plating particle 22, but incides transparent spraying plating particle 22 from abrasive surface.And a part for this light is formed on the reflection such as crystal boundary and hole of the periphery of spraying plating particle 22, the inside that sees through spraying plating particle 22 injects to outside.In addition, do not incided next spraying plating particle 22 by the light of the reflection such as crystal boundary and hole, similarly inject to outside through reflection, transmission.And in actual crystal boundary, on the basis of transmission, reflection, also produce scattering phenomenon, can realize the behavior of more complicated light.

The phenomenons such as such reflection of light, transmission and scattering can be given the light of this sputtered films of bismuth 1 uniqueness.This is because they are different in itself from the reflection of the coating overlay film of the polishing based on for example only possessing on surface etc., can realize gloss and the light with the degree of depth.By possessing this gloss and light, this sputtered films of bismuth 1 can become to possess sputtered films of bismuth unique reflecting feel of the degree of depth, that have extremely beautiful outward appearance.For example, be yttrium oxide (Y at metal oxide ₂o ₃), when aluminum oxide, present the extremely beautiful outward appearance that has white completely concurrently and have the reflecting feel of the degree of depth as ceramic whiteware.Such sputtered films of bismuth 1 has never been realized up to now, is brand-new coating overlay film.

Enforcement as described above grind the 2nd deposited metal 20 formation can with do not grind the 2nd deposited metal 20 identical in essence.The surperficial porosity of, having implemented the 2nd deposited metal grinding can be also more than 5% and below 15%.Same with the 2nd deposited metal 20 not grinding, by comprise the overlay film tissue of distinctive hole in sputtered films of bismuth, even if grind concavo-convex (representational is recess) that also can form appropriateness.It should be noted that, for example, the surface roughness Ra of the 2nd deposited metal before grinding is generally below 10 μ m, is preferably below 7 μ m, is particularly preferably below 4 μ m.Therefore, the grinding of the 2nd deposited metal can be for example so that the surface roughness Ra of the 2nd deposited metal be that 100nm is below for target is carried out.Be below 100nm by making surface roughness Ra, in the 2nd deposited metal 20 of above-mentioned form, can form suitable concavo-convexly, further improve light reflective.The sputtered films of bismuth 1 that possesses the 2nd deposited metal 20 can possess for example taking Grossmeters as more than 75 excellent lights.In addition simultaneously, by this concavo-convex existence, sense of touch, feel when people contacts this spraying plating overlay film improve, and then can realize appropriate skidproof effect.

Be below 100nm in order to make the surface roughness Ra of the 2nd deposited metal, preference is as effects on surface enforcement grinding.As Ginding process, it is not limited, abrasive cloth, the grinding pad etc. that for example can enumerating sends as an envoy to comprises abrasive grains, ground slurry etc. is in the method for the surface sliding of deposited metal.Grind and both can be undertaken also can being undertaken by multistep grinding steps more than two steps by single step grinding step, until the surfaceness of regulation.Especially in order to obtain high, the beautiful overlay film of aesthetic appearance, preferably in the grinding step more than two steps, carry out pre-grinding and smooth grinding (mirror ultrafinish) and progressively reduce surfaceness.

It should be noted that, said glossiness is 20 ° of gloss values herein, can measure according to JIS Z8741.To measuring the glossometer using, there is no particular limitation, can use known glossometer in the past.For example can use Konica Minolta Optics, trade(brand)name " GM-268Plus " or its similar product that Inc. manufactures are measured.

In addition, the surface roughness Ra in this specification sheets can be used known surfaceness form measuring instrument (for example TOKYO SEIMITSU CO., LTD. manufactures " SURFCOM1500DX " or its similar product) in the past to measure.Measure preferably under measured length 10mm for example, the finding speed 0.3mm/ condition of second and carry out.

It should be noted that, although there is no particular limitation, from same reason to described in the 2nd deposited metal 20 of not implementing to grind, the thickness that also preferably makes surface carry out the 2nd deposited metal 20 grinding is that 10 μ m are above and below 200 μ m.On the other hand, for the 2nd deposited metal 20 before grinding, prediction degree of grind, as suitable example, can illustrate and be made as in advance for example 200 μ m thickness above and left and right below 400 μ m.Thus, can not form the 2nd deposited metal 20 superfluously or grind, can realize easily gauge control thinner and guaranteed the sputtered films of bismuth 1 of aesthetic appearance.

Sputtered films of bismuth 1 as described above and the hardware 100 with overlay film can have the aesthetic appearance of excellence as above, and have for example, excellent chemistry, mechanical characteristics and overlay film adaptation from metal oxide (, aluminum oxide) concurrently.Especially, can mainly realize high closing force (overlay film adaptation), can realize excellent aesthetic appearance by the 2nd deposited metal 20 of above-mentioned specific formation by the 1st deposited metal 10 of above-mentioned specific formation.It should be noted that, aspect aesthetic appearance, from the past, can be used as target as the porcelain of artistic products, natural marble, grouan etc.In other words, the 1st deposited metal 10 can be realized the sputtered films of bismuth of densification and mechanical properties excellence, and the 2nd deposited metal 20 is grinding surperficial in the situation that, for example can realize, as such beautiful of porcelain (, ceramic whiteware), natural stone and be full of the outward appearance of feeling of high class.

It should be noted that, for above-mentioned aesthetic appearance, the situation such as main end user's sensation (for example, vision and sense of touch) is evaluated, and can depend on state of health, the mood of hobby, every day, fatigue.Therefore, for example, benchmark shown in can the table 1 based on following, evaluates (sensory test) to aesthetic appearance of the present invention more objectively.Particularly, for example about the sensory test of aesthetic appearance can based on people's (no matter having undisciplined participator) feel evaluate.And, be the following assessment item of sputtered films of bismuth for evaluation object, be categorized into corresponding to " well " " common ", any one of three grades of " poor ".Then evaluation (judgement) that, for example can be using the maximum grade of number of classification as this project about this sputtered films of bismuth.Number to participator has no particular limits, can be single can be also many people.Single in the situation that, preferably have about the experience of this evaluation or the people of training.

It should be noted that, (*) mark in table 1 is the evaluation that the sputtered films of bismuth to having ground surperficial form carries out.In addition, the benchmark of this judgement can suitably change according to purposes, the object etc. of the sputtered films of bismuth of the object as evaluating.For example, the expression such as " irregular colour is even ", " bright is inhomogeneous " is to the inhomogeneous judgement of not expecting, for give consciously sputtered films of bismuth " irregular colour is even ", " bright is inhomogeneous " taking raising aesthetic appearance as object for, not included in the object of described evaluation.

[table 1]

Table 1

In addition, for the adaptation of sputtered films of bismuth, for example can make sputtered films of bismuth 1 to the dhering strength of metal base 30 for for example more than 5MPa.This coating overlay film as commercial use is enough intensity for the adaptation of metal base.

This adaptation can preferably be measured based on the middle evaluation method of recording of for example explanation of JIS H8667:2002 sintering metal sputtered films of bismuth test method " 3.2 adaptation ".It should be noted that, in this manual, in the evaluation method of recording in above-mentioned explanation " 3.2 adaptation ", caking agent uses epoxy resin, be the crushing load (N) of measuring overlay film under 1mm/min at draw speed, adopt the value calculating by following formula as dhering strength.

Dhering strength (MPa)=crushing load (N)/bond area (mm ²)

On the other hand, though do not illustrate especially, in sputtered films of bismuth 1 of the present invention and the hardware 100 with overlay film, between the 1st deposited metal 10 and the 2nd deposited metal 20, possessing the middle deposited metal that form is different with above-mentioned specific form can be also suitable embodiment.This centre deposited metal, as long as the deposited metal that the spraying plating particle deposition taking metal oxide as main component forms, has no particular limits its form etc.

As this centre deposited metal, for example, along with moving from the 1st deposited metal 10 side direction the 2nd deposited metal 20 thrusters, the form of middle deposited metal can be from or similar form identical with the 1st deposited metal 10 to form identical with the 2nd deposited metal or similar metamorphosis.This variation can be stratified, can be also continuous variation.Possess the sputtered films of bismuth 1 of this oblique structure and the hardware 10 with overlay film by formation, can make overlay film organize more stable.

Above sputtered films of bismuth of the present invention 1 and the hardware 100 with overlay film can be that low sputtering process is made aptly by the impact that can control the molten state of melt granules and suppress melt granules while clashing into base material.To allowed impact, according to material, the form etc. of metal base 30 and different, must not make sweeping generalizations, especially in the time of the formation of the 1st deposited metal 10, by the condition such as surface temperature and flying distance, flight velocity of suitable control melt granules, can make aptly sputtered films of bismuth 1 and the hardware 100 with overlay film.As this sputtering process, might not be limited, for example, and as an example, the plasma body sputtering processs such as the plasma spraying method that the output inhibition can preferably list generation plasma body time is low low output etc.

For example can exemplify following method: particularly, using median size is that the alpha-alumina powder of 1 about μ m～30 μ m is as the spraying plating powder for the 2nd deposited metal 20, use median size than the aforementioned spraying plating powder for the 2nd deposited metal 20 large and median size be alpha-alumina powder about 15 μ m～50 μ m as the spraying plating powder for the 1st deposited metal 10, utilize low output plasma spraying method etc. to carry out spraying plating.Now, also considering to accelerate the translational speed (for example, 700mm/ second more than) of spray torch or make with respect to the spraying plating angle of metal base 30 is low angle (for example, 50 °) etc.Metal base 30 is that thickness is in the situation of thin plate of the aluminium alloy below 5mm, preferably from by the face of plating surface opposition side, this base material is carried out cooling.Beyond this cooling de-watering is cold, can also be undertaken cooling by suitable refrigeration agent.

It should be noted that, in the above-described embodiment, exemplify hole contained in sputtered films of bismuth 1 14,24 states at surface opening, but this opening (hole 14,24) for example can implement to utilize the sealing of hole processing of hole sealing agent.Kind to the hole sealing agent that can use has no particular limits, but more preferably uses the hole sealing agent of so-called mineral-type.As the hole sealing agent of this mineral-type, for example, can exemplify the hole sealing agent of organosilicon alkanes etc.In the case of grinding sputtered films of bismuth 1 surperficial, this sealing of hole processing can be carried out before grinding, and also can after grinding, carry out.

Below, to describing about embodiments of the invention, but and do not mean that the present invention is subject to the restriction of following examples.

［ with the hardware of overlay film ］

In present embodiment, by (1) aluminum oxide (Al ₂o ₃) powder, (2) yttrium oxide (Y ₂o ₃) powder, (3) mullite (Al ₆o ₁₃si ₂) powder utilizes respectively the spraying plating of plasma spraying method to the thin plate substrate of aluminium alloy system, thereby decorate application, make the hardware with overlay film.

As metal base, use the sheet material that is of a size of the aluminium alloy (A6061) that 50mm × 50mm and thickness are 5mm.Sputtered films of bismuth is made the bilayer structure being made up of the 1st deposited metal and the 2nd deposited metal, use respectively median size be (1) alpha-alumina powder, (2) yttrium oxide powder, (3) mullite powder of 25 μ m as the spraying plating powder that is used to form the 1st deposited metal, using median size is that (1) alpha-alumina powder, (2) yttrium oxide powder, (3) mullite powder of 10 μ m is as the spraying plating powder that forms the 2nd deposited metal.

Plasma spraying uses commercially available coating machine (Praxair Inc. manufacture, SG-100) to carry out.Argon gas from 0.34MPa to this coating machine that under atmospheric pressure supply with, as plasma body working gas, is supplied with the helium of 0.34MPa as secondary air, between negative electrode and anode, applies voltage, produces thus plasma body.Plasma generation condition during by spraying plating is made as plasma generation voltage 35.6V, electric current 900A.The feed rate that uses powder feeding machine (Praxair Inc. manufacture, Model1264) to divide with about 15g/ is supplied with spraying plating powder in this plasma body, make on one side spray torch move with the speed of 800mm/ second, on one side with spraying plating apart from 150mm, the plasma irradiating angle of base material be made as to 60 ° form sputtered films of bismuth.Thus, obtain possessing the hardware with overlay film 1～3 of the sputtered films of bismuth being formed by (1) aluminum oxide, (2) yttrium oxide, (3) mullite of the present invention.

The 1st deposited metal is the thickness that carries out plasma spray coating and form approximately 200 μ m on aluminum alloy base material with the spraying plating powder that the 1st above-mentioned deposited metal is used.In addition, the 2nd deposited metal is on the surface of the 1st deposited metal obtaining, and carries out plasma spray coating and forms the thickness of approximately 100 μ m with the spraying plating powder that the 2nd above-mentioned deposited metal is used.It should be noted that, in spraying plating, for the distortion of the thin plate substrate of the aluminium alloy system that prevents from being caused by plasma heat source and softening, from the back side, base material is carried out cooling.

It should be noted that, for relatively, under common spraying plating condition in the past, formed sputtered films of bismuth.; the alpha-alumina powder that only uses the 1st above-mentioned deposited metal to use, being made as spraying plating is 90 ° apart from 90mm, to the plasma irradiating angle of base material, other condition is same as described above; carry out plasma spraying, thereby on aluminum alloy base material, form the sputtered films of bismuth of the thickness of approximately 200 μ m.Be made into the hardware with overlay film of comparison.

［ evaluation ］

For the hardware 1 and 2 with overlay film of the present invention obtaining as described above, the feel that sputtered films of bismuth has the pure white of self-alumina or yttrium oxide and has fine-textured skin, presents the outward appearance that nature is gentle.For the hardware 3 with overlay film, sputtered films of bismuth presents shallow dark brown from mullite, has realized naturally gentle outward appearance.This mullite is owing to having used the mullite that trace comprises metal impurities in raw material, and therefore sputtered films of bismuth is not the color (white) that powdered material looks.It should be noted that, though not shown concrete example confirms using mullite as spraying plating powder in the situation that, according to the kind of impurity, amount, the hue adjustment of sputtered films of bismuth can be formed for such as grey～dark brown grade.In addition, in aluminum alloy base material, do not observe distortion etc., can be judged as high-quality decoration application.,, according to 10 valuators, aspect feel, outward appearance, color, the sputtered films of bismuth of the hardware 1～3 with overlay film all can be evaluated as " well ".

On the other hand, although the hardware with overlay film has relatively obtained coming the white sputtered films of bismuth of self-alumina, the melt granules can confirm due to spraying plating time clashes into impact and the heat of base material, and aluminum alloy base material bends.In addition, confirm concavo-convexly on the surface of sputtered films of bismuth, this concavo-convex depression that is considered to base material causes.Although this is concavo-convex is no problem level as the purposes such as coated film, the protective membrane of industrial member for large-scale member, the decoration application of the small-sized electric product of for example commercialization of conduct etc. is obvious.Although sputtered films of bismuth is relatively soft and beautiful white, poorer than sputtered films of bismuth of the present invention aspect skin texture.,, although the sputtered films of bismuth color of the hardware with overlay film relatively can be evaluated as " well ", feel and ocular estimate are " common " or " poor ".

The sputtered films of bismuth part of the above-mentioned hardware with overlay film 1 is carried out to the test of following project (1)～(3), investigate its characteristic.The results are shown in following table 2.It should be noted that, the hardware with overlay film relatively cannot carry out accurate evaluation due to the distortion of base material.

(1), for the 1st deposited metal, investigate average pore diameter and porosity in the cross section vertical with metal base.

(2) for the 2nd deposited metal, investigate surperficial average pore diameter and porosity.

(3) for the 1st deposited metal and the 2nd deposited metal, investigation Alpha-alumina shared ratio in the total of Alpha-alumina phase and gama-alumina phase.This ratio P α obtains as follows: by the result of the X-ray diffraction analysis (XRD) to the 1st deposited metal and the 2nd deposited metal, near the intensity of diffraction peak (2 θ=43 °) of (113) face that belongs to Alpha-alumina is made as to I α, near the intensity at peak (2 θ=45 °) of (400) face that belongs to gama-alumina is made as to I γ, obtain by above-mentioned formula (1) and (2).

(4), for the 1st deposited metal and the 2nd deposited metal, use small testing machine (Shimadzu Scisakusho Ltd manufacture, micro Vickers HMV-1) with hardness mark HV0.2(test force 1.961N) measure the Vickers' hardness in the cross section vertical with base material.Measuring point is made as 10 places.

[table 2]

Table 2

Sputtered films of bismuth of the present invention can confirm: the porosity near the 1st deposited metal of aluminum alloy base material is low, and the hole forming is in addition also little, has formed overlay film extremely fine and close compared with sputtered films of bismuth in the past.Although the hardness of overlay film, not as the sputtered films of bismuth of industrial use in the past, can confirm and show sufficiently high value in commercial use in addition.About the 2nd deposited metal, its porosity is high, and the hole forming is in addition also large, therefore known its lower hardness.Think that this is because spraying plating powder is finer.But obtaining at indentation load is 0.2(1.961N) time vickers hardness hv 300, can confirm the member that can serve as commercial use coated film and fully application.

［ surface grinding ］

Then, the hardware 1～3 with overlay film of the present invention obtained above is ground with the surface of the hardware with overlay film relatively.The grinding on surface is carried out as follows: use the ground slurry of the alumina particle that comprises median size 1.3 μ m as abrasive grains, carry out pre-grinding until surface roughness Ra is 300nm left and right, then use the ground slurry that comprises the colloid silica that particle diameter is 100nm, making surface roughness Ra is the mirror ultrafinish below 100nm.The grinding condition of mirror ultrafinish is as follows.

［ mirror ultrafinish condition ］

Shredder: Co., Ltd.'s this lathe of ridge is made made, sheet shredder (PNX-322)

Grind load: 15kPa

Dull and stereotyped rotating speed: 30rpm

Head rotating speed: 30rpm

Milling time: approximately 20 minutes

The temperature of ground slurry: 20 DEG C

The feed speed of ground slurry: 0.5 liter/min (use natural flow)

The hardware with overlay film 1～3 after mirror ultrafinish of the present invention all produces bright and clean light on its surface, becomes extremely beautiful and is full of the outward appearance of feeling of high class.In addition, the surface of the hardware 1 and 2 with overlay film possesses white and has the transparent feel of the degree of depth.For the hardware 3 with overlay film, sometimes become grey, dark brown sputtered films of bismuth according to the composition (kind of metallic impurity, amount) as the mullite of depositing materials.Such texture is the unique texture that cannot see in the coating overlay film that for example comprises resinous principle.For this hardware 1 with overlay film of the present invention, while measuring surfaceness and glossiness, can confirm that Ra50nm, glossiness are 70～100.In the time implementing the identical grinding of surfaceness (Ra) degree, the material that specific refractory power is high can obtain the sputtered films of bismuth of surperficial gloss excellence, and aesthetic appearance is also excellent.About the specific refractory power of the light of the wavelength 550nm of each depositing materials, yttrium oxide is 1.87, aluminum oxide is 1.76, mullite is 1.64, and the sputtered films of bismuth of the hardware 1～3 with overlay film has also obtained the roughly glossiness corresponding to this specific refractory power.Like this, for the sputtered films of bismuth of the hardware with overlay film 1～3 after grinding, by 10 valuators, aspect feel, outward appearance, color and reflecting feel, also can be evaluated as " well ".To the hardware with overlay film 1～3 after mirror ultrafinish, while confirming the thickness of the 2nd deposited metal, be approximately 20 μ m.

It should be noted that, though do not specifically illustrate in the present embodiment, when the sputtered films of bismuth only being formed by the 1st deposited metal is implemented to mirror ultrafinish, although obtain gloss on surface, sputtered films of bismuth is originally as transparent, and confirmation can see through it see aluminum alloy base material., the white of opaque beauty as above is thought what the scattering of light effect of the hole of the modest size by forming in the intergranular crystal boundary of the spraying plating based on the 2nd deposited metal, this crystal boundary obtained.

On the other hand, even if the hardware with overlay film relatively utilizes mirror ultrafinish also cannot obtain the such gloss of the hardware with overlay film of the present invention.Though its reason is not clear and definite, can think to form depression by spraying plating on the surface of base material and not show the formation state of crystal boundary in reflecting feel, sputtered films of bismuth tissue, hole inappropriate.

Above, describe the present invention according to suitable embodiment, but obviously this explanation non-limiting item can be carried out various changes.

Claims (20)

1. a sputtered films of bismuth, it deposits the sputtered films of bismuth forming for spraying plating particle taking metal oxide as main component on metal base,

This sputtered films of bismuth, possessing the 1st deposited metal with the region of described base material adjacent, possesses the 2nd deposited metal in the surperficial region that comprises described sputtered films of bismuth,

The surperficial porosity of described the 2nd deposited metal is more than 5% and below 15%.

2. sputtered films of bismuth according to claim 1, wherein, the porosity in the cross section vertical with substrate surface of described the 1st deposited metal is more than 2% and below 20%.

3. sputtered films of bismuth according to claim 1 and 2, wherein, the median size of the spraying plating particle exposing on described surface of described the 2nd deposited metal is more than 1 μ m and below 30 μ m.

4. according to the sputtered films of bismuth described in any one in claim 1～3, wherein, the average pore diameter in described the 1st cross section vertical with surface described metal base deposited metal is more than 1 μ m and below 15 μ m.

5. according to the sputtered films of bismuth described in any one in claim 1～4, wherein, the average pore diameter in described the 2nd cross section parallel with surface described metal base deposited metal is more than 1 μ m and below 20 μ m.

6. according to the sputtered films of bismuth described in any one in claim 1～5, wherein, the thickness of described the 1st deposited metal is more than 20 μ m and below 400 μ m.

7. according to the sputtered films of bismuth described in any one in claim 1～6, wherein, the thickness of described the 2nd deposited metal is more than 10 μ m and below 400 μ m.

8. according to the sputtered films of bismuth described in any one in claim 1～7, wherein, grind on the surface of described the 2nd deposited metal.

9. sputtered films of bismuth according to claim 8, wherein, the surface roughness Ra of described the 2nd deposited metal is below 100nm.

10. sputtered films of bismuth according to claim 8 or claim 9, wherein, the glossiness on described surface is more than 75.

11. according to the sputtered films of bismuth described in any one in claim 1～10, and wherein, described metal oxide is aluminum oxide.

12. sputtered films of bismuth according to claim 11, wherein, in described the 1st deposited metal,

By in the X-ray diffraction analysis of the 1st deposited metal, from the diffracted intensity of (113) face of Alpha-alumina be made as I α, while being made as I γ from the diffracted intensity of (400) face of gama-alumina, by following formula (1):

Pα1（%）=Iα/（Iα+Iγ）×100···（1）

Defined Alpha-alumina one after another P α 1 is more than 8% and below 25%.

13. according to the sputtered films of bismuth described in claim 11 or 12, wherein, and in described the 2nd deposited metal,

By in the X-ray diffraction analysis of the 2nd deposited metal, from the diffracted intensity of (113) face of Alpha-alumina be made as I α, while being made as I γ from the diffracted intensity of (400) face of gama-alumina, by following formula (2):

Pα2（%）=Iα/（Iα+Iγ）×100···（2）

Defined Alpha-alumina one after another P α 2 is below 7%.

14. 1 kinds of hardwares with overlay film, wherein, the sputtered films of bismuth in the surface of metal base possesses claim 1～13 described in any one.

15. hardwares with overlay film according to claim 14, wherein, described metal base is aluminium or its alloy.

16. according to the hardware with overlay film described in claims 14 or 15, and wherein, the thickness of described metal base is below 5mm.

17. according to the hardware with overlay film described in any one in claim 14～16, and wherein, described metal base has carried out surface roughening, and described metal base and described sputtered films of bismuth are by physical construction and integrated.

18. according to the hardware with overlay film described in any one in claim 14～17, and wherein, described sputtered films of bismuth is more than 5MPa to the dhering strength of described metal base.

19. according to the hardware with overlay film described in any one in claim 14～18, its outer exterior material that is electric product.

20. 1 kinds possess using the article of the part of exterior material outside at least of the hardware with overlay film described in any one in claim 14～19.