CN103938144B - Sputtered films of bismuth and metal component with overlay film - Google Patents
Sputtered films of bismuth and metal component with overlay film Download PDFInfo
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- CN103938144B CN103938144B CN201410022457.2A CN201410022457A CN103938144B CN 103938144 B CN103938144 B CN 103938144B CN 201410022457 A CN201410022457 A CN 201410022457A CN 103938144 B CN103938144 B CN 103938144B
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Abstract
The present invention provides a kind of sputtered films of bismuth and the metal component with overlay film, the excellent texture and tone that there is the sputtered films of bismuth porcelain to be shown, and the mechanical properties such as the adaptation to substrate, hardness also can be achieved at the same time.Manufacture a kind of sputtered films of bismuth, it is sputtered films of bismuth made of being deposited on metal base with metal oxide spraying plating particle as main component, the sputtered films of bismuth has the 1st deposited metal in the region with base material adjacent, has the 2nd deposited metal in the region on the surface comprising sputtered films of bismuth, the porosity on the surface of the 2nd deposited metal is 5% or more and 15% or less.
Description
Technical field
The present invention relates to sputtered films of bismuth and with the metal component of overlay film.More specifically, it is related to the spraying plating formed by spraying plating
Film and has the metal component with overlay film of the sputtered films of bismuth on surface.
Background technique
New functional technology is assigned by the way that overlay film is arranged on blocky substrate is still being applied to various fields so far.
Metallikon as one of dry overlay film (dry coating) technology is that (representative is by metal oxide by metal, ceramics
Manufactured oxide-based ceramic), the spraying plating powder of cermet (cermet) etc. by meltings such as combustion flame or electric energy simultaneously
Accelerate the melt granules, the surface of blocky substrate is blowed and sprayed and makes its deposition, to form the gimmick of overlay film.
Wherein, using the spray technique of the ceramic powders of plasma spraying method etc. due to can be both economical and at high speed
In the form of thick film to substrate assign ceramic material speciality, that is, heat resistance, abrasion performance, corrosion resistance and resistance to insulating properties etc. this
The excellent chemical machinery characteristic of sample, therefore it is widely used in jet engine, gas-turbine unit, paper roller processed, pump shaft
Deng the metal member towards general industry.In addition, in recent years, which is also applied to lead in medical semiconductor
The metal member etc. of equipment used in domain, above-mentioned additional function can be more accurately achieved.
The functionality of ceramic sputtered films of bismuth has been generally acknowledged that and is improved by the following method: improve melt granules between and substrate
Binding force between melt granules simultaneously inhibits porosity lower and realizes fine and close overlay film.Furthermore, it is believed that the sputtered films of bismuth is logical
Crossing (1) melts spraying plating powder completely, eliminates non-melt granules, (2) make the melt granules of flight have big acceleration and with
Strong impact energy hits the surface of substrate and is realized (for example, referring to patent document 1).
Existing technical literature
Patent document
Patent document 1: No. 2007/023976 specification of International Publication No.
Summary of the invention
Problems to be solved by the invention
However, the above-mentioned ceramic sputtered films of bismuth using plasma spraying method is merely used as general industry purposes so far.That is,
Actual conditions are the coating overlay films for being absolutely not used as electric product towards ordinary consumer etc..This is because so far
The function that the coating overlay film of electric product towards ordinary consumer etc. requires is mainly aesthetic appearance and adaptation, representative to be
The coated film that is formed by coated film, metal-plated overlay film for being formed by organic materials such as various resins etc. by metal material or by
Resin is met with the effect that the coated film etc. that inorganic or metal material composite material is formed is realized.
On the other hand, for example, in electric product towards ordinary consumer etc., from miniaturization and high intensity
From the point of view of the reasons such as taking into account, being cost effective, it is desirable that the coating overlay film covering higher by mechanical property, thinner of outer exterior material.For example, needing
With the covering of the protective film of high mechanical strength light weight and with thin plate made of thermal diffusivity but the slightly worse aluminium alloy of mechanical property.
In addition, about the coating overlay film to machine towards ordinary consumer etc., the coating overlay film i.e. in commercial use, also potentially phase
The new aesthetic appearance of the vision to be achieved for appealing to people.
However status is, wraps resiniferous coated film and although provides diversified film, but their heat resistance and
Mechanical strength inequality.Although more excellent by the overlay film mechanical strength that metal material is formed, aesthetic appearance is defined to metal
(metallochrome) appearance, such as cannot correspond to want to obtain and naturally feel such and require.In addition, about above-mentioned ceramics spray
Plated film does not provide any functional technology for improving this one side of aesthetic appearance.
In particular, for example using the thin plate of aluminium alloy as substrate applications in the case where above-mentioned plasma spraying method,
Since the mechanical strength of substrate becomes lower, due to presence as the percussion (peening) caused by the shock of spraying plating particle
The problem of being deformed in substrate itself.In addition, by the thermal expansion system in the substrate of the ceramic sputtered films of bismuth and aluminium alloy formed
The difference of number is big, it may thus be appreciated that can cause to generate warpage such problems in the substrate because of the heat affecting in spraying plating.It needs to illustrate
Although leading to the problem of in previous ceramic spray technique for the recess of this undesirable substrate, warpage is to be not intended as
Level, but from the point of view of this one side of aesthetic appearance when, is likely to become great problem.That is, this is because in the presence of for example to delicate
The worry that light degree of reflection has an impact or energy is ground in damage when grinding the sputtered films of bismuth.
The present invention is made in view of this aspect, and its purpose is to provide have both the completely new of aesthetic appearance and mechanical property
Ceramic sputtered films of bismuth.In addition, another object of the present invention is to provide the metal components with overlay film for having the sputtered films of bismuth.
The solution to the problem
To achieve the goals above, sputtered films of bismuth provided by the present invention is with metal oxide spraying plating as main component
Sputtered films of bismuth made of grain deposits on metal base.And the sputtered films of bismuth has the 1st in the region adjacent with above-mentioned metal base
Deposited metal has the 2nd deposited metal in the region on the surface comprising above-mentioned sputtered films of bismuth.And, which is characterized in that above-mentioned 2nd spraying plating
The porosity on the surface of layer is 5% or more and 15% or less.
That is, sputtered films of bismuth present invention as described above is substantially made of metal oxide, have not comprising such as resin etc.
Machine material, metal material.Therefore, artificial (plastics) texture that ice-cold, the resin having with metal product have is completely not
Together, distinctive natural feeling (texture) and feel (sense of touch) in such as ware can be built.In addition, basic herein
On, moreover it is possible to obtain having both the product of chemical characteristic and mechanical property excellent possessed by ceramics.
Such aesthetic appearance and chemical machinery characteristic can be by having originally from the metal oxide for constituting sputtered films of bismuth
Some characteristics are realized, and can be passed through above-mentioned specific 2nd deposited metal and be realized attractive appearance.Specifically, the 2nd deposited metal is being ground
In the case where having ground surface, it is configured to can be achieved to have been assigned the spray of the aesthetic appearance of the unique reflecting feel with depth
Coating.Such sputtered films of bismuth is have never been realized so far, completely new coating overlay film, is provided for the first time by the present invention.
It should be noted that " main component " refers to includes with the ratio of 97 mass % or more in the composition in this specification
The meaning of the ingredient, it is representative to refer to comprising 99 mass % or more, preferably 99.5 mass % or more, more preferably 99.7 matter
Measure the ingredient of % or more (for example, 99.9 mass % or more).
In addition, be characterized in that in a preferred embodiment for sputtered films of bismuth disclosed herein, above-mentioned 1st deposited metal
Porosity in the section vertical with substrate surface is 2% or more and 20% or less.
By the 1st deposited metal of above-mentioned specific modality, it mainly can inhibit the impact to substrate and realize that high closing force (covers
Film adaptation).Specifically, the flexibility and adaptation to substrate when the 1st deposited metal can be realized spraying plating, and realize mechanical
The sputtered films of bismuth of excellent.
In a preferred embodiment for sputtered films of bismuth disclosed herein, be characterized in that, above-mentioned 2nd deposited metal above-mentioned
The average grain diameter for the spraying plating particle that surface is exposed is 1 μm or more and 30 μm or less.
According to this constitution, the surface of sputtered films of bismuth is formed by the spraying plating particle with average grain diameter as described above, it is possible to provide
More improve the sputtered films of bismuth of distinctive natural feeling in ware etc., aesthetic appearance as feel.
In a preferred embodiment for sputtered films of bismuth disclosed herein, be characterized in that, above-mentioned 1st deposited metal with it is above-mentioned
Average pore diameter in the vertical section in the surface of metal base is 1 μm or more and 15 μm or less.
By making the size of the hole above range in the 1st deposited metal, can be realized makes the mechanical strength of sputtered films of bismuth more
Add raising.
In a preferred embodiment for sputtered films of bismuth disclosed herein, be characterized in that, above-mentioned 2nd deposited metal with it is above-mentioned
Average pore diameter in the parallel section in the surface of metal base is 1 μm or more and 20 μm or less.
By making the size of the hole above range of the 2nd deposited metal, higher aesthetic appearance can be realized.For example, grinding
When grinding the sputtered films of bismuth, it can be realized and be not only tone or even reflecting feel, bright all with depth, extremely beautiful coating is covered
Film.
In a preferred embodiment for sputtered films of bismuth disclosed herein, be characterized in that, above-mentioned 1st deposited metal with a thickness of
20 μm or more and 400 μm or less.
The thickness of 1st deposited metal gets over Bao Zeyue it is possible to realize lightweight, but then cannot sufficiently to obtain overlay film close for excessive thinning
Conjunction property and mechanical property.Therefore, it by making the thickness of the 1st deposited metal be in above-mentioned range, can be realized thickness control
Sputtered films of bismuth that is thinner and ensuring adaptation and mechanical property.
In a preferred embodiment for sputtered films of bismuth disclosed herein, be characterized in that, above-mentioned 2nd deposited metal with a thickness of
10 μm or more and 400 μm or less.
The thickness of 2nd deposited metal gets over Bao Zeyue, and it is possible to realize lightweights, but since the transmittance of the light of the 1st deposited metal is high,
In order not to appear metal base, the 2nd deposited metal needs the thickness of appropriateness.In addition, the reality on the surface of aftermentioned grinding sputtered films of bismuth
It applies in mode, preferably in advance in view of forming the 2nd deposited metal by thickness that grinding removes.From the point of view of the viewpoint, pass through
The 2nd deposited metal is adjusted in above-mentioned range, can easily realize the thinner of thickness control and not influence the face of substrate
The high sputtered films of bismuth of the aesthetic appearance of color.
In a preferred embodiment for sputtered films of bismuth disclosed herein, be characterized in that, the surface of above-mentioned 2nd deposited metal into
Grinding is gone.
By grinding the surface of above-mentioned 2nd deposited metal, the excellent aesthetic appearance of sputtered films of bismuth of the invention becomes more significant,
So it is preferred that.That is, feeling gentle for the sputtered films of bismuth for the form that surface is ground and being put by irradiation light
It is bright out, thus can realize with just like the extremely beauty that the porcelain of artistic products is mutually equal to appearance.Or, it can be achieved that with natural
The grand beauty that stone, the mineral facies referred to as so-called jewel, pyroxene etc. for appreciating and decorating are equal to.More specifically,
For example, when metal oxide is aluminium oxide, can become almost pure white and by light irradiation release it is unique it is bright,
The appearance as ceramic whiteware device.It should be noted that the 1st essence of the deposited metal based on the spraying plating particle formed by metal oxide
Characteristic and be transparent, therefore, it is considered that the aesthetic appearance is mainly to be realized by the composition of the 2nd deposited metal.In addition, for example for
For ceramic whiteware device, glass transparent and with glossiness is covered on the surface of being formed by kaolin, pure white and hard blank
The aspect of the glaze of matter and the composition of sputtered films of bismuth of the invention are entirely different.Therefore, by this composition, the color with depth is provided
Adjust (for example, white) and the extremely beautiful of reflecting feel, completely new coating overlay film.
In a preferred embodiment for sputtered films of bismuth disclosed herein, it is characterized in that, the surface of above-mentioned 2nd deposited metal is thick
Rugosity Ra is 100nm or less.
Above-mentioned 2nd deposited metal in sputtered films of bismuth even if grinding by that, comprising the overlay film tissue of distinctive hole, can also form
The bumps of appropriateness.Think to realize that the light reflective of superior gloss as described above is improved by being properly formed the bumps.
Such as the excellent light for being 75 or more with Grossmeters may be implemented.In addition simultaneously, by the presence of the bumps, contacted in people
Sense of touch, feel when the sputtered films of bismuth improve, and then appropriate antiskid effect also may be implemented.
It in a preferred embodiment for sputtered films of bismuth disclosed herein, is characterized in that, above-mentioned metal oxide is oxidation
Aluminium (alumina).
Above-mentioned sputtered films of bismuth can and constituting the composition of metal oxide of the sputtered films of bismuth to its tone (form and aspect) into
The various adjustment of row.And especially when above-mentioned metal oxide is aluminium oxide, such as it can be realized almost white spray
Plated film.In other words, more preferred in terms of it can realize texture that is pure white and having fine-textured skin as ceramic whiteware.
In a preferred embodiment for sputtered films of bismuth disclosed herein, it is characterized in that, it, will in above-mentioned 1st deposited metal
The diffracted intensity in (113) face in the X-ray diffraction analysis of the 1st deposited metal, from Alpha-alumina is set as I α, from γ-oxygen
When the diffracted intensity in (400) face of change aluminium is set as I γ, by following formula (1):
P α 1(%)=I α/(I α+I γ) × 100(1)
Defined Alpha-alumina one after another P α 1 is 8% or more and 25% or less.
Spraying plating powder when spraying plating can be mutually indicated with Alpha-alumina included in aluminium oxide spraying plating particle as main component
End not sufficiently melting.1st deposited metal of this composition is to make Alpha-alumina mutually have adjusted spray in such a way that above-mentioned ratio is remaining
The state of melt granules when plating.That is, more appropriately suppressed impact energy possessed by melt granules when hitting substrate
With sputtered films of bismuth is formed in the state of heat.Therefore, sputtered films of bismuth of the invention can be used as further reduced in substrate generate recess,
The sputtered films of bismuth of the worry of warpage and provide.
In a preferred embodiment for sputtered films of bismuth disclosed herein, it is characterized in that, it, will in above-mentioned 2nd deposited metal
The diffracted intensity in (113) face in the X-ray diffraction analysis of the 2nd deposited metal, from Alpha-alumina is set as I α, from γ-oxygen
When the diffracted intensity in (400) face of change aluminium is set as I γ, by following formula (2):
P α 2(%)=I α/(I α+I γ) × 100(2)
Defined Alpha-alumina one after another P α 2 is 7% or less.
When 2nd deposited metal of this composition has adjusted spraying plating in a manner of the above-mentioned ratio of residual quantity for making Alpha-alumina phase
The state of melt granules.That is, most of melting of melt granules when hitting substrate, the mutual adaptation of spraying plating particle more
Sputtered films of bismuth is formed in the state of raising.Therefore, sputtered films of bismuth of the invention can be formed as the spraying plating particle in the region comprising surface
The plated film that mutual adaptation is improved.
In addition, the metal component with overlay film provided according to the present invention is characterized in that, in Metal Substrate in other sides
The surface of material has above-mentioned any sputtered films of bismuth.
It is known that previous by metal oxides such as aluminium oxide to be formed if carrying out direct spraying plating to the metal base of steel etc.
Manufactured sputtered films of bismuth is then unable to get sufficient closing force.Therefore, in order to improve the closing force, usually metal base and by
The basal layer formed by metal is set between the sputtered films of bismuth that metal oxide is formed, this is indispensable (for example, referring to patent
Document 1).However, for example by keeping the particle for constituting the 1st deposited metal for example flat and the biggish spraying plating particle of partial size, it can
Adaptation forms above-mentioned sputtered films of bismuth well, and it is hereby ensured that the adaptations that require on the way of such as business.
Thus, it is possible to provide have the sputtered films of bismuth of on the basis of adaptation and mechanical property aesthetic appearance also excellent pottery
Metal component.Such as, it is possible to provide it builds the metallicity component for the feel having fine-textured skin as ware and then has
The color of depth, metal component with extremely beautiful appearance.
In a preferred embodiment for metal component with overlay film disclosed herein, it is characterized in that, above-mentioned Metal Substrate
Material is aluminium or its alloy.
Aluminium and its alloy have been light weight, excellent thermal conductivity, therefore Recent study among metal material as personal
The use of the outer exterior material of the electric products such as computer, mobile phone etc..However, aluminium or its alloy on the other hand there is also be easy by
The disadvantage such to damage.However, the mechanical strength of above-mentioned sputtered films of bismuth, such as can be high rigidity.Therefore, by adopting
Use the component formed by aluminium or its alloy as the substrate of the metal component of the invention with overlay film, it can be to the substrate of the aluminium system
Excellent mechanical strength is assigned, advantages of the present invention can be more effectively played, so it is preferred that.
In a preferred embodiment for metal component with overlay film disclosed herein, it is characterized in that, above-mentioned Metal Substrate
Material with a thickness of 5mm or less.
Above-mentioned sputtered films of bismuth can using reduce the Impact energy of the metal oxide particle as spraying plating raw material state,
And the temperature of the melt granules of the metal oxide is suppressed to low state, the surface of metal base is hit, thus shape
At.Therefore, even if when using thickness than relatively thin sheet metal as substrate, the metal with overlay film also can suitably be obtained
Component is without making substrate deformation.In particular, even if also can suitably be obtained when being made with a thickness of the substrate of 5mm aluminium system below
To the metal component with overlay film.
In a preferred embodiment for metal component with overlay film disclosed herein, it is characterized in that, above-mentioned Metal Substrate
Material has carried out surface roughening, and above-mentioned metal base is integrated by mechanical structure with above-mentioned sputtered films of bismuth.
To the metal base of surface roughening has been carried out in advance, above-mentioned sputtered films of bismuth is formed using spraying plating, thus, it is possible to
Obtain the metal component with overlay film that the adaptation of metal base and sputtered films of bismuth sufficiently improves.For example, sputtered films of bismuth pair can be obtained
The dhering strength of metal base is the metal component of 5MPa or more.Thus, it can be achieved that aesthetic appearance, mechanical property and film adaptation
The metal component with overlay film that any one is realized with high level.
As described above, the metal component provided by the present invention with overlay film has by metal oxide (so-called oxide
Class ceramics) sputtered films of bismuth that is formed, therefore it can be substantially heat resistance, abrasion performance, corrosion resistance and resistance to insulating properties or the like
The metal component of excellent chemical machinery excellent.On this basis, the metal component provided by the present invention with overlay film
It also achieves and has excellent aesthetic appearance.Therefore, the component of the various articles of commercial use can be preferably used as.For example, energy
Enough as article providing general consumer, requiring attractive appearance and hobby property, such as with various electric products, culinary art
The residential equipments such as the building materials such as the life groceries such as utensil, panel, various electricity generation systems be outer exterior material of article etc. of representative etc. and
It properly uses.In particular, can be preferably used as requiring the electricity as properties such as the high intensity of outer exterior material, thermal diffusivity and insulating properties
The outer exterior material of gas product.As the electric product, as its an example can example go out mobile phone, PC and its periphery and set
Standby, TV, blue ray recorder, the AVC such as camera equipment, stereo equipment, the AV such as automobile navigation equipment, refrigerator, air-conditioning, air are clear
Beauty health-cares equipment such as the consumer electricals such as clean machine equipment, hair dryer etc..
Detailed description of the invention
Fig. 1 is the sectional view for schematically showing the composition of the metal component with overlay film an of embodiment.
Fig. 2 is the sectional view for schematically showing the composition of the metal component with overlay film of other embodiment.
Description of symbols
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
100, the 100a metal components with overlay film
Specific embodiment
Hereinafter, referring to attached drawing appropriate, based on suitable embodiment to sputtered films of bismuth of the invention and with the metal of overlay film
Component is illustrated.It should be noted that other than as the item (feature etc. of sputtered films of bismuth) especially mentioned in this specification
Thing necessary to item, of the invention implementation (for example, the composition of coating apparatus, application method of the coating apparatus etc.) can
To be held as based on the prior art in the field, those skilled in the art customary means.The present invention can be based on this
Content disclosed in specification is implemented with the common technical knowledge in the field.In addition, in each figure size relationship (length, width,
Thickness etc.) substantially indicate sputtered films of bismuth and the metal component with overlay film of the invention form feature, reality might not be reflected
Size relationship in the sputtered films of bismuth on border and the metal component with overlay film.
[ composition of the metal component with overlay film ]
Fig. 1 is the sectional view for schematically showing the composition of the metal component with overlay film an of embodiment.It is disclosed herein
The metal component 100 with overlay film for example as shown in Figure 1, having sputtered films of bismuth 1 on the surface of metal base 30.
As the material for constituting metal base 30, it is not particularly limited, is able to use various metal materials.Such as it can show
Example is the heat-resisting alloy of representative for the steel of representative, with inconel (Inconel) etc. with various SUS materials etc. out, with invar
Alloy (Invar), Kovar alloy (Kovar) etc. are the low-expansion alloy of representative, with Hastelloy
It (Hastelloy) etc. is the corrosion resisting alloy of representative, using as the 1000 useful series such as lightweight construction material~7000 series
Aluminium alloy etc. is the aluminium alloy etc. of representative.Melt granules when sputtered films of bismuth 1 of the invention can reduce spraying plating are to metal base 30
Impact when shock and heat and formed.Therefore, when using aluminum or aluminum alloy as metal base 30, especially aluminium alloy is being used
Thin plate in the case where, the speciality of the metal component 1 of the invention with overlay film becomes obviously, so particularly preferably.The aluminium alloy
Thin plate for example can be with a thickness of 5mm or less, such as 3mm hereinafter, 1mm or less may further be limited to.Hereinafter, to use
The thin plate of aluminium alloy as metal base 30 in case where be illustrated.
Though Fig. 1 is not shown, metal base 30 can also be for example, by the chemical hand such as the physics such as sandblasting processing gimmick, etching
Method makes the surface roughening for having sputtered films of bismuth 1.That is, small bumps also can be set on the surface of metal base 30.It is logical
The surface for so destroying metal base 30 in advance is crossed, sputtered films of bismuth 1 enters in the bumps on the surface of metal base 30, Metal Substrate
Material 30 is mechanically firmly combined with sputtered films of bismuth 1.To configuration of surface realized by the roughening treatment etc. without special
Limitation, such as can example send as an envoy to metal base 30 surface roughness Ra be 0.2 μm~20 μm or so.
Also, the sputtered films of bismuth 1 is by depositing on above-mentioned metal base 30 with metal oxide spray as main component
Particle 12,22 is plated to constitute.More specifically, which has the 1st deposited metal in the region adjacent with metal base 30
10, in addition, having the 2nd deposited metal 20 in the region on the surface comprising sputtered films of bismuth 1.It is exemplified in present embodiment by the 1st spraying plating
The case where sputtered films of bismuth 1 for the double-layer structure that the 10 and the 2nd deposited metal 20 of layer is formed.As long as it should be noted that with metal base 1
Adjacent region has the 1st deposited metal 10, has the 2nd deposited metal 20 in the region on the surface comprising sputtered films of bismuth 1, then can also be
Has the deposited metal of other forms between 1st deposited metal 10 and the 2nd deposited metal 20.
Herein, as the metal oxide for constituting spraying plating particle 12,22, there is no particular limitation, can be set to various gold
The oxide of category.As the metallic element of the composition metal oxide, such as can enumerate selected from B, Si, Ge, Sb, the eka-golds such as Bi
Category element, 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,
The transition metal elements such as Mn, Fe, Co, Ni, Cu, Ag, Au, La, Ce, Pr, Nd, Er, a kind or 2 kinds in the lanthanide series such as Lu with
On.Particularly preferably it is 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, such as MgO, CaO, SrO, Sc can be enumerated2O3, Y2O3, La2O3,
TiO2, ZrO2, HfO2, VOX(such as V2O5Deng), Nb2O3, Ta2O5, CrOX(such as Cr2O4Deng), WOX(such as WO2、WO3Deng),
MnOX(such as MnO, MnO2、Mn3O4Deng), FeOX, CoOX, NiO, CuO, AgO, ZnO, Al2O3, MgAl2O4, Al6O13Si2、
Ga2O3, In2O3, SnO2, BiOX, CeO2, PrOX, Nd2O3, Er2O3, Lu2O3, ZrSiOX, ZrAlOX, HfSiOX, HfAlOX,
TiSiXOY, B2O3, SiO2, GeO2, Sb2O5Deng.
The composition of the metal oxide is it is contemplated that assigning the desired characteristic of sputtered films of bismuth 1 and suitably determining.The characteristic
It can refer to the physical characteristics such as the mechanical property such as hardness, toughness, refractive index, thermal conductivity, conductivity, fusing point, chemical-resistant resistance
Aesthetic appearances such as chemical characteristics, pattern, the tones such as property etc..Above-mentioned metal oxide both can with a kind be separately formed spraying plating particle 12,
22, it in addition can also combine two or more and constitute spraying plating particle 12,22.For example, including two or more metal in spraying plating particle 12,22
In the case where oxide, part or all of these oxides can also form composite oxides.In turn, for above-mentioned gold
For belonging to oxide, for example, for adjustment sputtered films of bismuth 1 tone purpose, as from used raw material (natural material)
Substance etc. also may include the element (for example, Na, K, Rb etc.) other than above-mentioned example.In addition, constituting the element of above-mentioned oxide
Can also in the form of ion etc. and by comprising.
Hereinafter, the suitable embodiment as sputtered films of bismuth disclosed herein, using metal oxide as aluminium oxide
(Al2O3) in case where, the feature of sputtered films of bismuth of the invention is described in detail.
1st deposited metal 10 is mainly deposited by flat spraying plating particle 12 as seen in common sputtered films of bismuth
It constitutes.In addition, the 2nd deposited metal 20 as seen in common sputtered films of bismuth, is mainly deposited by flat spraying plating particle 22
And it constitutes.Moreover, the periphery in the spraying plating particle 12,22 can form hole 14,24.
Herein, the porosity in the section vertical with 30 surface of substrate of the 1st deposited metal 10 be preferably 2% or more and 20% with
Under.
The presence of hole 14,24 in sputtered films of bismuth 1 can mechanical property to overlay film 1 and adaptation produce bigger effect.
In sputtered films of bismuth 1 of the invention, by the way that the porosity in the section vertical with the surface of substrate 30 of the 1st deposited metal 10 is inhibited
For 20% hereinafter, to inhibit the substrate 30 as caused by the difference of the 1st deposited metal 10 and the thermal expansion coefficient of substrate 30 warpage, and
And ensure high adhesion to substrate 30.In order to inhibit the warpage of substrate 30, the porosity of preferably the 1st deposited metal 10 be set as 2% with
On, representative is 5% or more, such as can be set to 10% or more.However, reducing or covering there are adaptation when porosity is excessively high
The worry that film hardness reduces, so not preferably.From the point of view of this aspect, the porosity of the 1st deposited metal 10 is set as 20% or less.Hole
It is 18% hereinafter, for example can be 15% or less that rate is representative.
Herein, the porosity about the 1st deposited metal 10 is by the section group substantially vertical with substrate 30 to sputtered films of bismuth 1
The observation image knitted carries out image analysis and the value that finds out.Specifically, being cut into the thickness side of the metal component 100 with overlay film
To arbitrary section, and with regulation multiplying power the micro- sem observation section in sputtered films of bismuth 1(for example, the 1st deposited metal 10)
Tissue, to observation image obtained from this carry out by hole portion and solid fraction from 2 values, and use image analysis software
It analyzes it, thus, it is possible to measure porosity.It should be noted that in the present specification, the measurement of porosity is as follows
It carries out: according to based on scanning electron microscope (SEM；Hitachi High-Technologies Corporation. system
Make, S-3000N) observation image (can be suitably any one of secondary electron image, composograph or radioscopic image.), it uses
Image analysis software (NIPPON ROPER K.K. manufacture, Image-Pro Plus) carries out image analysis.
It should be noted that the form for the hole 14,24 for including in sputtered films of bismuth 1 depends on the deposition of spraying plating particle 12,22
State, thus it is sometimes different with its situation on horizontal direction in the direction vertical relative to substrate 30.Vertical with substrate 30
Section on evaluation about the porosity of the 1st deposited metal 10 be based on following opinion: the porosity evaluated by the section is more
Add the adaptation and heat shrinkability characteristic for influencing the 1st deposited metal 10.
When hole 14 contained in 1st deposited metal 10 includes macrovoid on a small quantity, the intensity of the 1st deposited metal 10 is because of the hole
14 and part reduce, so not preferably.Therefore, the average pore diameter of hole 14 contained in the 1st deposited metal 10 is preferably 1 μm
Above and 15 μm or less.
In this specification, the average pore diameter about the 1st deposited metal 10, which refers to, cuts vertical with the surface of substrate 30
The defined direction of hole 14 in face is measured the average value (determining direction average diameter) of resulting diameter.The average pore
Diameter carries out the observation image of the section structure of 1st deposited metal 10 substantially vertical with substrate 30 in the same manner as above-mentioned porosity
Image analysis and find out.For example, about the hole portion for having carried out 2 values to the observation image prepared as described above, measurement regulation
Direction aperture sections size and be averaged, so as to find out.It should be noted that in this specification, average hole
The measurement of gap diameter carries out as follows in the same manner as the measurement of above-mentioned porosity: according to based on scanning electron microscope (SEM；
Hitachi High-Technologies Corporation. manufacture, S-3000N) observation image (can be suitably secondary electricity
Any one of son picture, composograph or radioscopic image.), using image analysis software (NIPPON ROPER K.K. manufacture,
Image-Pro Plus) carry out image analysis.
The 1st above deposited metal 10 can be to inhibit impact, heat affecting of the melt granules to metal base 30 with only
The peripheral part of spraying plating powder melts and central part does not melt deposited metal made of such, lower condition spraying plating of Impact energy.
Simultaneously as being deposited with the state that the peripheral part of spraying plating powder sufficiently melts, it is thus ensured that spraying plating particle 12 is to metal
The adaptation and the mutual adaptation of melt granules 12 of substrate 30.For example, can be with the 1st deposited metal 10 made of the condition spraying plating
It is suitably formed the extremely fine and close tissue that porosity is 2% or more and 20% or less (for example, 2% or more and 5% or less).
Herein, for the molten condition of the spraying plating particle 12 in the 1st deposited metal 10, in the portion for the non-molten condition not melted
Divide in the total of the part (hereinafter referred to as puddle) of (hereinafter referred to as non-puddle) and the molten condition temporarily melted, does not melt
Ratio shared by part can be suppressed to defined ratio.
Ratio shared by the non-puddle for example can by using image analysis software to the 1st deposited metal 10 and base
The observation image of the vertical section structure of material 30 is analyzed to hold.That is, finding out the spraying plating particle 12 in the 1st deposited metal 10
The area of the area of puddle and non-puddle, according to they can calculate non-puddle shared by ratio.It needs
Bright, the area of the area of the puddle of spraying plating particle 12 and non-puddle can for example obtain as follows: with regulation times
The microscope pair of rate is observed with the tissue in the section vertical with substrate 30 of the 1st deposited metal 10, to thus resulting observation
Image is carried out puddle using image analysis software and does not melt 2 values being partially separated, and respective area is calculated.It needs
Illustrate, for the spraying plating particle 12 of the 1st deposited metal 10, when puddle and not melting is partially separated, visual image
When, the part for not remaining the shape of original spraying plating powder and flat shape being presented can be judged as puddle, it will be residual
Stay the central part of original spraying plating powder and the part of the shape that maintains particle is judged as non-puddle.
Ratio shared by such non-puddle for operating and finding out is preferably substantially 1% or more and 25% or less.
On the other hand, the molten condition of the spraying plating particle 12 depends on the type of metal oxide, but also can be according to example
Constitute the ratio of the crystal phase of metal oxide such as to confirm.For example, the 1st deposited metal 10 is comprising based on aluminium oxide (alumina)
When wanting constituent of the ingredient as spraying plating particle 12, the Alpha-alumina of high-temperature stable phase and γ-oxygen of low-temperature phase can be passed through
Change the ratio of aluminium to confirm.The alumina particle usually used as spraying plating powder is the alpha-oxidation that crystal structure is hexagonal crystal system
Aluminium, alumina particle chilling after melting, so that Alpha-alumina transformation (phase transformation) is the gama-alumina of cubic system.The 1st
In deposited metal 10 Alpha-alumina exist with ratio as described above be because are as follows: i.e., it is possible to indicate that spraying plating particle does not melt completely,
Representative is the meaning nearby to there is the mutually remaining state deposition of Alpha-alumina in its center.
In the 1st deposited metal 10, Alpha-alumina phase ratio shared in the total of Alpha-alumina phase and gama-alumina phase
Such as it can be used as Alpha-alumina one after another (P α 1) and find out indirectly as follows.That is, P α 1 is the value acquired as follows: carrying out to the 1st
The X-ray diffraction (XRD) of deposited metal is analyzed, and the diffracted intensity in (113) face from Alpha-alumina is set as I α, from γ-oxygen
When the diffracted intensity in (400) face of change aluminium is set as I γ, with P α 1(%)=I α/(I α+I γ) × 100 values found out.It needs to illustrate
Be, in the present specification, X-ray diffraction analysis using X-ray diffraction device (Rigaku Corporation manufacture,
UltimaIV).
It should be noted that Alpha-alumina (can be non-fusing department) is shared for example when metal oxide is aluminium oxide
Ratio for example can using the situation that above-mentioned P α 1 is 8% or more as preferably, more preferably 10% or so or more, it is further excellent
It is selected as 12% or so or more.However, the surplus ratio (can be non-melt rate) of Alpha-alumina, which excessively will lead to spraying plating powder, to be filled
Divide melting, so not preferably.From the point of view of this aspect, above-mentioned P α 1 can be for example 25% or less by ratio shared by Alpha-alumina
The case where as preferably, more preferably 20% or less, be further suitable for being set as 18% or less.
It should be noted that the metal oxide for constituting spraying plating powder usually can be crystallinity height, to visible transparent
Substance.Therefore, the 1st deposited metal 10 with above tissue and metal oxide particle (for example, alumina particle) script
Characteristic it is same, it is seen that the transmittance of light is high and can be transparent.That is, a large amount of formed not will lead to light between spraying plating particle 12
Scattering degree larger crystal boundary, hole 14.Moreover, adaptation admirably deposits spraying plating particle 12 each other.In this way, being
The central part of spraying plating powder is set not melt when aluminium oxide (for example, remain Alpha-alumina phase) and peripheral part melting ground, closely sealed
Property admirably deposits spraying plating particle 12, such as the use of biggish spraying plating powder is suitable.Due to the tissue morphology pole of sputtered films of bismuth 1
It is complicated, and therefore, it is difficult to the shapes and sizes of specific spraying plating particle 12, such as representative is that the 1st deposited metal 10 can be
Partial size biggish spraying plating particle 12 deposition and constitute.Such 1st deposited metal 10 for example can be by using average grain diameter
For 20 μm or more 40 μm spraying plating powder below plasma spraying and be suitably formed.Thereby, it is possible to ensure metal base
30 is extensive with the contact area of spraying plating particle 12, realizes the 1st excellent deposited metal 10 such as adaptation and film-strength.
In addition, though being not particularly limited, but the thickness of the 1st deposited metal 10 is preferably set to 20 μm or more and 400 μm or less.
The thickness of 1st deposited metal 10 gets over Bao Zeyue, and it is possible to realize lightweights.Therefore, the thickness of the 1st deposited metal 10 is more preferably set as 350 μm
Hereinafter, for example can be set to 300 μm or less.If being unable to fully be covered however, the thickness of the 1st deposited metal 10 becomes too thin
Film adaptation and mechanical property.Therefore, the thickness of the 1st deposited metal 10 be preferably set to 50 μm or more, for example can be set to 100 μm with
On.Thereby, it is possible to realize the thinner of thickness control and ensure the sputtered films of bismuth 1 of adaptation and mechanical property.
On the other hand, it is assigned and making porosity 5% or more and 15% or less on surface of the 2nd above-mentioned deposited metal 20
Feature.
The presence of hole 14,24 in sputtered films of bismuth 1 can mechanical property to overlay film 1 and adaptation affect greatly.
In sputtered films of bismuth 1 of the invention, by the way that the porosity on the surface of the 2nd deposited metal 20 is limited to above range, so that it is guaranteed that spraying plating
The mutual adhesion strength of particle 22 and realize higher appearance.It is as described above excellent in order to have in sputtered films of bismuth 1
Aesthetic appearance, the porosity of the 2nd deposited metal 20 must be set as 5% or more, typically preferably 6% or more, for example can be 8%
More than.However, excessively high porosity can damage the dhering strength of the 2nd deposited metal 20, film intensity.From the point of view of this aspect, the 2nd spray
The porosity of coating 20 is set as 15% or less.Porosity is preferably 13% or less, can be for example 11% or less.
In addition, the porosity about the 2nd deposited metal 20 is to carry out figure by the observation image of the surface texture to sputtered films of bismuth 1
The value found out as analysis.Specifically, with the surface for the micro- sem observation sputtered films of bismuth 1 for providing multiplying power (that is, the 2nd deposited metal 20
Surface) tissue, to obtained observation image carry out by hole portion and solid fraction from 2 values, and use image analysis
Software analyzes it, and thus, it is possible to measure porosity.It should be noted that in the present specification, to about the 2nd deposited metal
The measurement of 20 porosity is also to carry out as follows: according to based on scanning electron microscope (SEM；Hitachi High-
Technologies Corporation. manufacture, S-3000N) observation image (can be suitably secondary electron image, composograph
Or any one of radioscopic image.), use image analysis software (NIPPON ROPER K.K. manufacture, Image-Pro
Plus image analysis) is carried out.
It should be noted that carrying out evaluation on its surface to the porosity about the 2nd deposited metal 20 is seen based on following
Solution: the porosity evaluated by the surface can produce bigger effect the aesthetic appearance of sputtered films of bismuth 1.
2nd deposited metal 20 more preferably sputtered films of bismuth 1 surface expose spraying plating particle 22 average grain diameter be 1 μm or more and
30 μm or less.That is, the 2nd deposited metal 20 is the layer of the Porous comprising hole 24, configuration of surface can be for the recessed of appropriateness
Convex form, the appropriate bumps are formed and with the particle of the average grain diameter of above range.It needs to illustrate
It is that spraying plating particle 22 is same as metal oxide particle, substantially the transmittance of visible light is high and can be transparent, but light is at it
Surface scatters, so that human eye will not see substrate through it.
Therefore, above-mentioned range is in by the average grain diameter and the porosity of the 2nd deposited metal 20 that make spraying plating particle 22,
2 deposited metals 20 show with the corresponding colors such as the scattering situation of the composition of metal oxide and light, can be at by its configuration of surface
To have natural feeling, the form of feel that the blank etc. of ware is shown.For example, being aluminium oxide in metal oxide
When, the 2nd deposited metal 20 show it is similarly white with alumina powder, can have parian ware blank shown it is pure white
And has the feel having fine-textured skin.The average grain diameter of spraying plating particle 22 is preferably 5 μm or more, can be for example 10 μm or more.Separately
The average grain diameter of outer spraying plating particle 22 is preferably 25 μm or less, can be for example 20 μm or less.Such 2nd deposited metal 20 is for example
It can be suitable for landform by using the plasma spraying that average grain diameter is 1 μm or more and 20 μm spraying plating powder below
At.
It is surveyed it should be noted that average grain diameter refers to by the particle size distribution device based on laser light scattering diffraction approach
The partial size (50% volume average particle size) of accumulated value 50% in fixed size distribution.In the present specification, the measurement of average grain diameter
The value obtained using the laser diffraction/scattering formula granulometry device " LA-300 " for using Horiba Ltd to manufacture.
It should be noted that in the present specification, the average grain diameter for the spraying plating particle 22 of sputtered films of bismuth 1 exposed on surface is
Refer to average value (the fixed side of the diameter measured on the defined direction of seen spraying plating particle 22 when observing the surface of sputtered films of bismuth 1
To average diameter).For the average grain diameter, by the surface of the micro- sem observation sputtered films of bismuth 1 with defined multiplying power (that is, the 2nd spraying plating
Layer 20 surface) tissue and obtained observation image is measured.In this specification, in the spraying plating that surface is exposed
The measurement of the average grain diameter of grain 22 is done as follows: according to based on scanning electron microscope (SEM；Hitachi High-
Technologies Corporation. manufacture, S-3000N) observation image (can be suitably secondary electron image, composograph
Or any one of radioscopic image.), use image analysis software (NIPPON ROPER K.K. manufacture, Image-Pro
Plus image analysis) is carried out.It should be noted that about 2 values, such as can be by being set in above-mentioned image analysis software
Upper limit threshold (such as 130) and lower threshold (such as 0) are appropriately carried out.
However, porous sputtered films of bismuth often becomes, the mutual combination of spraying plating particle 22 is weak, sputtered films of bismuth of mechanical properties.Cause
This almost melts preferably as the metal oxide particle of depositing materials and is deposited in the 2nd deposited metal 20.For example,
It, can be with as ratio P α 2 shared by the Alpha-alumina (non-fusing department) in the 2nd deposited metal 20 when metal oxide is aluminium oxide
It is found out in the same manner as with above-mentioned 1st deposited metal 10 the case where.That is, P α 2 is following value: carrying out the X-ray diffraction to the 2nd deposited metal
(XRD) it analyzes, the diffracted intensity in (113) face from Alpha-alumina is set as I α, (400) face from gama-alumina is spread out
When penetrating intensity and being set as I γ, with P α 2(%)=I α/(I α+I γ) × 100 values found out.Moreover, as spraying plating particle 22 composition at
In the aluminium oxide divided, Alpha-alumina ratio shared in the total of Alpha-alumina and gama-alumina is as P α 2, preferably 7%
Below.That is, the alumina particle as depositing materials is almost melted and is deposited.Therefore, spraying plating particle 22 can be with almost
The state adaptation melted completely is attached to well on the 1st deposited metal 10, and also adaptation is well each other for spraying plating particle 22
Mutually it be combined with each other.Ratio shared by the Alpha-alumina (non-fusing department) is as P α 2, preferably 5% hereinafter, further preferably 3%
Below.
In turn, for hole 24 contained in the 2nd deposited metal 20, when comprising excessive gap, the intensity of the 2nd deposited metal 20
Due to the hole 24, part is reduced, so not preferably.Therefore, the average pore diameter for the hole 24 that the 2nd deposited metal 20 includes
Preferably 1 μm or more and 20 μm or less.
The average pore diameter of 2nd deposited metal 20 can with above-mentioned 1st deposited metal 10 the case where in the same manner as find out.
Though the 2nd spray can be exemplified as preferred example as an embodiment in addition, there is no particular limitation
The thickness of coating 20 is set as 10 μm or more and 200 μm or less.Due to the 1st deposited metal 10 be it is transparent, in order to prevent penetrate its
See metal base 30 and the thickness of the 2nd deposited metal 20 is set as 10 μm or more.The thickness is more preferably 20 μm or more, such as can
To be set as 50 μm or more.However, the 2nd deposited metal 20 if than it is required it is thicker if be difficult to seek lightweight, therefore for example preferably will
Thickness is set as 200 μm hereinafter, being further set as 150 μm hereinafter, for example can be set to 100 μm or less.It will be thick thereby, it is possible to realize
Degree control is thinner and ensure the sputtered films of bismuth 1 of aesthetic appearance.
Fig. 2 is the composition for schematically showing the metal component 100a with overlay film on ground surface an of embodiment
Sectional view.As illustrated in the Fig. 2, the surface of the 2nd deposited metal 20 has carried out grinding and sputtered films of bismuth 1 of the invention and with overlay film
The suitable embodiment of metal component 100a.The grinding is more preferably mirror ultrafinish.If to the surface of the 2nd deposited metal (that is, spray
The surface of plated film 1) it is ground, then the spraying plating particle 22 positioned at surface is partially pruned and exposes abradant surface.Herein, it carries out
The spraying plating particle 22 of grinding and the spraying plating particle 22 existing for its periphery can show optical unique effect.
That is, light does not reflect on the surface of spraying plating particle 22, but the spraying plating particle of the transparency is incident on from abradant surface
22.Also, a part of the light is formed on the reflection such as crystal boundary and hole of the periphery of spraying plating particle 22, through spraying plating particle 22
Inside inject to outside.In addition, not being incident on next spraying plating particle 22 by the light of the reflections such as crystal boundary and hole, similarly pass through
Reflection transmits and injects to outside.And in actual crystal boundary, scattering phenomenon is also generated on the basis of transmission, reflection, it can be with
Realize the behavior of more complicated light.
Phenomena such as reflection, transmission and scattering of such light, can assign the unique light of sputtered films of bismuth 1.This is because
It is different in itself from the reflection etc. of the coating overlay film based on the polishing for example only having on surface, may be implemented with depth
Gloss and light.By having the gloss and light, which can become the unique reflecting feel for having depth
, sputtered films of bismuth with extremely beautiful appearance.For example, being yttrium oxide (Y in metal oxide2O3), aluminium oxide when, show
The extremely beautiful appearance of complete white and the reflecting feel for having depth is had both as ceramic whiteware.Such sputtered films of bismuth 1 is so far
It only has never been realized, is completely new coating overlay film.
Constituting for the 2nd deposited metal 20 for implementing grinding as described above can be with the 2nd deposited metal 20 that does not grind
It is identical in matter.That is, the porosity for implementing the surface of the 2nd deposited metal of grinding may be 5% or more and 15% or less.With do not grind
2nd deposited metal 20 of mill is same, by including the overlay film tissue of distinctive hole in sputtered films of bismuth, can also be formed even if grinding suitable
The bumps of degree (representative is recess portion).It should be noted that for example, the surface roughness Ra of the 2nd deposited metal before grinding is logical
Often for 10 μm hereinafter, preferably 7 μm hereinafter, particularly preferably 4 μm or less.Therefore, the grinding of the 2nd deposited metal can for example so that
The surface roughness Ra of 2nd deposited metal is that the following are targets to carry out by 100nm.By making surface roughness Ra 100nm hereinafter,
Bumps appropriate can be formed in the 2nd deposited metal 20 of above-mentioned form, further raising light reflective.Has the 2nd spray
The excellent light that it is for example 75 or more with Grossmeters that the sputtered films of bismuth 1 of coating 20, which can have,.In addition simultaneously, pass through the bumps
In the presence of sense of touch, i.e. feel when people contacts the spray coating improves, and then can realize appropriate antiskid effect.
In order to make the surface roughness Ra 100nm of the 2nd deposited metal hereinafter, it is preferred that for example implementing to grind to surface.As
Grinding method, to it, there is no restrictions, such as can enumerate the send as an envoy to abrasive cloth comprising abrasive grains, grinding slurry etc., grinding pad
Deng the method slided on the surface of deposited metal.Grinding both can by single step grinding process carry out and also by two steps more than
Multistep grinding process carries out, until defined surface roughness.Especially for the overlay film that aesthetic appearance is high, beautiful is obtained, preferably exist
Pre-grinding and smooth grinding (mirror ultrafinish) are carried out in grinding process more than two steps and gradually reduce surface roughness.
It should be noted that glossiness described herein is 20 ° of gloss values, can be measured according to JIS Z8741.
There is no particular limitation for the glossometer used measurement, and known glossometer can be used.It can be used for example
The trade name " GM-268Plus " of Konica Minolta Optics, Inc. manufacture or its be measured similar to product.
In addition, known surface roughness form measuring instrument can be used in the surface roughness Ra in the specification
(such as TOKYO SEIMITSU CO., LTD. manufacture " SURFCOM1500DX " or its similar to product) is measured.Measurement preferably exists
Such as it measured length 10mm, carries out under conditions of finding speed 0.3mm/ seconds.
It should be noted that, although there is no particular limitation, but from to being not carried out described in the 2nd deposited metal 20 of grinding
Same reason is set out, it is also preferred that the 2nd deposited metal 20 for grinding surface with a thickness of 10 μm or more and 200 μm with
Under.On the other hand, for the 2nd deposited metal 20 before grinding, prediction degree of grinding can show and set in advance as suitable example
For such as 200 μm or more and 400 μm or less Zuo You of thickness.The 2nd deposited metal 20 will not be excessively formed as a result, or is ground
Mill can be realized thickness control easily thinner and ensure the sputtered films of bismuth 1 of aesthetic appearance.
Sputtered films of bismuth 1 as described above and the metal component 100 with overlay film can have excellent appearance as described above
Property, and have both excellent chemistry, mechanical property and overlay film adaptation from metal oxide (for example, aluminium oxide).In particular,
High closing force (overlay film adaptation) can be mainly realized, by above-mentioned specific by above-mentioned the 1st deposited metal 10 specifically constituted
The 2nd deposited metal 20 constituted can realize excellent aesthetic appearance.It should be noted that in terms of aesthetic appearance, as artistic products
Porcelain, natural marble, granite etc. can be used as target from the past.In other words, the 1st deposited metal 10 can realize it is fine and close and
The excellent sputtered films of bismuth of engineering properties, the 2nd deposited metal 20 in the case where having ground surface, it can be achieved that as porcelain (for example, ceramic whiteware),
Beauty as natural stone and the appearance for being full of feeling of high class.
It should be noted that for above-mentioned aesthetic appearance, the feeling (for example, vision and tactile) of main user is commented
Valence may rely on hobby, daily health status, mood, the situations such as fatigue.It may be thus possible, for example, to be based on 1 institute of table below
The benchmark shown is more objectively evaluated (sensory test) to aesthetic appearance of the invention.Specifically, for example about aesthetic appearance
Sensory test can be felt to evaluate based on people (no matter having undisciplined participant).Also, evaluation object is sprayed
Following assessment items of plated film, be categorized into correspond to " good ", " common ", three grades of " poor " any one.It then, such as can
Evaluation (judgement) of the grade most using the number that will classify as the project about the sputtered films of bismuth.Do not have to the number of participant
There is special limitation, can be one and be also possible to more people.In the case where one, preferably about the experience of the evaluation or instruction
Experienced people.
It should be noted that (*) label in table 1 is the evaluation carried out to the sputtered films of bismuth for the form for having ground surface.
In addition, the benchmark of the judgement can be suitably changed according to purposes, the purpose etc. of the sputtered films of bismuth of the object as evaluation.Example
Such as, " uneven color ", " bright is uneven " etc. indicate the non-uniform judgement to not expecting, for being to improve aesthetic appearance
Purpose and for assigning sputtered films of bismuth " uneven color ", " bright is uneven " consciously, do not include pair in the evaluation
As in.
[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 example
5MPa or more.This is enough intensity for the adaptation of metal base as the coating overlay film of commercial use.
The adaptation can the explanation based on such as JIS H8667:2002 cermet sputtered films of bismuth test method " 3.2 is close
The evaluation method recorded in conjunction property " preferably measures.It should be noted that in the present specification, " 3.2 is close for above-mentioned explanation
In the evaluation method recorded in conjunction property ", bonding agent uses epoxy resin, measures the disconnected of overlay film in the case where tensile speed is 1mm/min
Load (N) is split, using the value calculated by following formula as dhering strength.
Dhering strength (MPa)=breaking load (N)/bond area (mm2)
On the other hand, though being not particularly illustrated, in sputtered films of bismuth 1 of the invention and metal component 100 with overlay film,
Have form between 1 deposited metal 10 and the 2nd deposited metal 20 and the different intermediate deposited metal of above-mentioned specific form is also possible to fit
Suitable embodiment.Spraying plating made of as long as the intermediate deposited metal is deposited with metal oxide spraying plating particle as main component
Layer, then be not particularly limited its form etc..
As the intermediate deposited metal, for example, with from 10 side of the 1st deposited metal to 20 side of the 2nd deposited metal elapse, intermediate spraying plating
The form of layer can be from the form same or similar with the 1st deposited metal 10 to the shape same or similar with the 2nd deposited metal
The form of state variation.The variation, which can be, to have levels, and is also possible to continuously to change.Has this oblique structure by being formed
Sputtered films of bismuth 1 and metal component 10 with overlay film, overlay film tissue can be made more stable.
Above sputtered films of bismuth 1 of the invention and the metal component 100 with overlay film can be by can control the molten of melt granules
Impact when melting state and melt granules being inhibited to hit substrate is low metallikon suitably to make.Impact to being allowed,
It is different according to the material of metal base 30, form etc., it must not make sweeping generalizations, especially in the formation of the 1st deposited metal 10, lead to
The conditions such as surface temperature and flying distance, the flying speed of suitable control melt granules are crossed, 1 He of sputtered films of bismuth can be suitably made
Metal component 100 with overlay film.It as the metallikon, might not be limited, for example, as an example, preferably arranging
It enumerates and output when generating plasma is suppressed to plasmas metallikons such as the low plasma spraying method of low output etc..
Such as can example go out following method: specifically, the use of average grain diameter being 1 μm~30 μm or so of alpha-alumina
Spraying plating powder of the end as the spraying plating powder for being used for the 2nd deposited metal 20, using average grain diameter than being previously used for the 2nd deposited metal 20
Greatly and average grain diameter be 15 μm~50 μm or so alpha-alumina powder be used as the 1st deposited metal 10 spraying plating powder, utilization
Low output plasma spraying method etc. carries out spraying plating.At this time, it is also considered that accelerate the movement speed of spray torch (for example, 700mm/ seconds
More than) or make spraying plating angle low angle (for example, 50 °) etc. relative to metal base 30.Metal base 30 be with a thickness of
In the case where the thin plate of 5mm aluminium alloy below, preferably the substrate is cooled down from the face for being plated face opposite side.This is cold
But it in addition to water cooling, can also be cooled down by refrigerant appropriate.
It should be noted that in the above-described embodiment, example goes out hole 14,24 contained in sputtered films of bismuth 1 on surface
The state of opening, but the sealing pores using hole sealing agent for example can be implemented in the opening (hole 14,24).To the envelope being able to use
The type of hole agent is not particularly limited, but more preferably uses the hole sealing agent of so-called inorganic.As the hole sealing agent of the inorganic,
Such as can example go out the hole sealing agent etc. of organosilicon alkanes.In the case where grinding the surface of sputtered films of bismuth 1, which can be
It carries out, can also be carried out before grinding after milling.
Hereinafter, being illustrated to about the embodiment of the present invention, but it is not meant to the present invention by following embodiment
It limits.
[ metal component with overlay film ]
In present embodiment, by (1) aluminium oxide (Al2O3) powder, (2) yttrium oxide (Y2O3) powder, (3) mullite
(Al6O13Si2) powder is utilized respectively in plasma spraying method spraying plating to thin plate substrate made of aluminum alloy, to carry out decoration painting
Dress makes the metal component with overlay film.
As metal base, using having a size of 50mm × 50mm and with a thickness of the plate of the aluminium alloy of 5mm (A6061).Spray
The double-layer structure being made of the 1st deposited metal and the 2nd deposited metal is made in plated film, (1) α-oxygen for the use of average grain diameter being respectively 25 μm
Change aluminium powder, (2) yttrium oxide powder, (3) mullite powder as the spraying plating powder for being used to form the 1st deposited metal, uses
(1) alpha-alumina powder, (2) yttrium oxide powder, (3) mullite powder that average grain diameter is 10 μm are sprayed as forming the 2nd
The spraying plating powder of coating.
Plasma spraying is carried out using commercially available coating machine (Praxair Inc. manufacture, SG-100).Under atmospheric pressure
The argon gas for supplying 0.34MPa to the coating machine supplies the helium of 0.34MPa as secondary gas as plasma working gas
Body applies voltage between a cathode and an anode, thus generates plasma.Plasma Production conditions when by spraying plating are set as
Gas ions generate voltage 35.6V, electric current 900A.Using powder supply machine (Praxair Inc. manufacture, Model1264) with about
15g/ points of supply amount supplies spraying plating powder into the plasma, moves spray torch with 800mm/ seconds speed
It is dynamic, on one side with spraying plating distance 150mm, 60 ° be set as to the plasma irradiating angle of substrate form sputtered films of bismuth.It obtains as a result,
The metal component with overlay film for having the sputtered films of bismuth of the invention formed by (1) aluminium oxide, (2) yttrium oxide, (3) mullite
1~3.
1st deposited metal is to carry out plasma spray coating with the spraying plating powder of the 1st above-mentioned deposited metal on aluminum alloy base material
And the thickness of about 200 μm of formation.In addition, the 2nd deposited metal is on the surface of the 1st obtained deposited metal, with the 2nd above-mentioned deposited metal
Spraying plating powder carries out plasma spray coating and forms about 100 μm of thickness.It should be noted that in spraying plating, for prevent by etc.
The deformation and softening of thin plate substrate made of aluminum alloy caused by ion body heat source, cool down from the back side by substrate.
It should be noted that foring sputtered films of bismuth under the conditions of previous usual spraying plating to compare.That is, being used only upper
The alpha-alumina powder for the 1st deposited metal stated is set as spraying plating distance 90mm, to the plasma irradiating angle of substrate is 90 °,
Other conditions are same as described above, plasma spraying carried out, to form the spray of about 200 μm of thickness on aluminum alloy base material
Plated film.It is made into the metal component with overlay film compared.
[ evaluation ]
For the metal component 1 and 2 of the invention with overlay film obtained as described above, sputtered films of bismuth, which has, carrys out self-alumina
Or yttrium oxide pure white and the feel having fine-textured skin, show the gentle appearance of nature.For the metal component 3 with overlay film, spray
Plated film, which is showed, realizes the gentle appearance of nature from the shallow dark brown of mullite.The mullite is due to using
The micro mullite comprising metal impurities in the feed, therefore sputtered films of bismuth is not that the color that seems of dusty material is (white
Color).It confirms it should be noted that though concrete example is not shown in the case where using mullite as spraying plating powder,
It can be to be formed such as grey~dark brown by the hue adjustment of sputtered films of bismuth according to the type of impurity, amount.In addition, being closed in aluminium
Deformation etc. is not observed in auri material, can determine whether the decoration coating for high quality.That is, according to 10 estimators, in feel, outside
It sees, the aspect of color, the sputtered films of bismuth of the metal component 1~3 with overlay film can be evaluated as " good ".
On the other hand, although the metal component with overlay film compared has obtained coming the sputtered films of bismuth of the white of self-alumina, but
Melt granules when confirming due to spraying plating hit the impact and heat of substrate, and aluminum alloy base material bends.In addition, in spraying plating
The surface of film confirms bumps, which is considered as caused by the recess of substrate.Although the bumps are as to large-scale structure
It is the level that there is no problem for the coated film of part, the purposes such as protective film of industrial component, but as example commercial small-sized
It is apparent for the decoration coating of electric product etc..Although the sputtered films of bismuth compared is soft and beautiful white, but in skin texture
Aspect is poorer than sputtered films of bismuth of the invention.Although that is, the sputtered films of bismuth color of the metal component with overlay film compared can be evaluated as it is " good
It is good ", but feel and ocular estimate are " common " or " poor ".
Following project (1)~(3) test is carried out to the spraying plating membrane part of the above-mentioned metal component 1 with overlay film, is adjusted
Look into its characteristic.It the results are shown in following tables 2.It should be noted that the metal component with overlay film compared is due to substrate
It deforms and accurate evaluation can not be carried out.
(1) for the 1st deposited metal, the average pore diameter and porosity in the section vertical with metal base are investigated.
(2) for the 2nd deposited metal, the average pore diameter and porosity on surface are investigated.
(3) for the 1st deposited metal and the 2nd deposited metal, Alpha-alumina is investigated mutually in Alpha-alumina phase and gama-alumina phase
Shared ratio in total.Ratio P α is found out as follows: by the X-ray diffraction analysis to the 1st deposited metal and the 2nd deposited metal
(XRD) as a result, by the intensity of the diffraction maximum (near 2 θ=43 °) in (113) face for belonging to Alpha-alumina be set as I α, will ownership
Intensity in the peak (near 2 θ=45 °) in (400) face of gama-alumina is set as I γ, is found out by above-mentioned formula (1) and (2).
(4) for the 1st deposited metal and the 2nd deposited metal, small hardness tester (Shimadzu Scisakusho Ltd's system is used
Make, micro Vickers HMV-1) with hardness mark HV0.2(test force 1.961N) dimension in the measurement section vertical with substrate
Family name's hardness.Measuring point is set as at 10.
[table 2]
Table 2
Sputtered films of bismuth of the invention can be confirmed: the porosity close to the 1st deposited metal of aluminum alloy base material is low, is additionally formed
Hole it is also small, form compared with previous sputtered films of bismuth extremely fine and close overlay film.Although in addition the hardness of overlay film is not as good as previous
Industrial use sputtered films of bismuth, but can be confirmed and show the sufficiently high value in commercial use.About the 2nd deposited metal,
Porosity is high, and the hole being additionally formed is also big, it may thus be appreciated that its hardness reduces.It is thought that because spraying plating powder is finer.
However, obtain indentation load be 0.2(1.961N) when vickers hardness hv 300, can confirm can be as the structure of commercial use
The coated film of part and sufficiently apply.
[ surface grinding ]
Then, by the metal component 1~3 of the invention with overlay film obtained above and the metal component with overlay film compared
Surface ground.The grinding on surface carries out as follows: using the grinding slurry of the alumina particle comprising 1.3 μm of average grain diameter
As abrasive grains, pre-grinding is carried out until surface roughness Ra is 300nm or so, then using comprising partial size is 100nm's
The grinding slurry of colloidal silicon dioxide carries out making surface roughness Ra 100nm mirror ultrafinish below.The grinding of mirror ultrafinish
Condition is as follows.
[ mirror ultrafinish condition ]
Grinder: Co., Ltd.'s this lathe of ridge makes made, Sheet-like abrasive machine (PNX-322)
Grind load: 15kPa
Plate revolving speed: 30rpm
Head revolving speed: 30rpm
Milling time: about 20 minutes
The temperature of grinding slurry: 20 DEG C
The feed speed of grinding slurry: 0.5 liter/min (being flowed using nature)
The metal component 1~3 with overlay film after mirror ultrafinish of the invention generates bright and clean light on its surface, becomes
Appearance that is extremely beautiful and being full of feeling of high class.In addition, the surface of the metal component 1 and 2 with overlay film has white and has depth
Transparent feel.For the metal component 3 with overlay film, according to the composition (kind of metal impurities for the mullite for being used as depositing materials
Class, amount) and become grey, dark brown sputtered films of bismuth sometimes.Such texture is in the coating overlay film for example comprising resin component
The unique texture that can not be seen.For the metal component 1 of the invention with overlay film, surface roughness and glossiness are measured
When, it can confirm that Ra50nm, glossiness are 70~100.In the identical grinding of implementation surface roughness (Ra) degree, refractive index is high
Material can obtain surface excellent gloss sputtered films of bismuth, and aesthetic appearance is also excellent.Wavelength 550nm about each depositing materials
Light refractive index, yttrium oxide 1.87, aluminium oxide 1.76, mullite 1.64, the metal component 1~3 with overlay film
Sputtered films of bismuth also obtained corresponding roughly to the glossiness of the refractive index.In this way, for the metal component 1 with overlay film after grinding
~3 sputtered films of bismuth can also be evaluated as " good " in terms of feel, appearance, color and reflecting feel by 10 estimators.
It is about 20 μm when confirming the thickness of the 2nd deposited metal to the metal component 1~3 with overlay film after mirror ultrafinish.
Though it should be noted that not specifically illustrated in the present embodiment, the sputtered films of bismuth implementation to only being formed by the 1st deposited metal
When mirror ultrafinish, although obtaining gloss on surface, as transparent, confirmation can pass through it and sees aluminum alloy base material sputtered films of bismuth sheet.
That is, opaque beautiful white as described above is considered through the intergranular crystal boundary of spraying plating, the crystalline substance based on the 2nd deposited metal
Obtained from the dispersion effect of the light of the hole of the modest size formed in boundary.
On the other hand, the metal component with overlay film compared is unable to get band of the invention using mirror ultrafinish and covered
Gloss as the metal component of film.Though its reason is not known, it is believed that forming recess on the surface of substrate by spraying plating
It is inappropriate that reflecting feel, the crystal boundary in spraying plating membrane tissue, the formation state of hole are not showed.
More than, according to suitable embodiment, the present invention is described, it is apparent that the explanation and non-limiting item, it can
To carry out various changes.
Claims (18)
1. a kind of metal component with overlay film, wherein have sputtered films of bismuth on the surface of metal base, the sputtered films of bismuth is with metal
Sputtered films of bismuth made of oxide spraying plating particle as main component deposits on metal base,
The sputtered films of bismuth has the 1st deposited metal in the region with the base material adjacent, in the region on the surface comprising the sputtered films of bismuth
Have the 2nd deposited metal,
Porosity in the section vertical with substrate surface of 1st deposited metal be 2% or more and 20% hereinafter,
The porosity on the surface of the 2nd deposited metal be 5% or more and 15% hereinafter,
The average grain diameter for the spraying plating particle of 2nd deposited metal exposed on the surface is 1 μm or more and 30 μm or less.
2. the metal component according to claim 1 with overlay film, wherein the 1st deposited metal with the metal base
The vertical section in surface in average pore diameter be 1 μm or more and 15 μm or less.
3. the metal component according to claim 1 with overlay film, wherein the 2nd deposited metal with the metal base
The parallel section in surface in average pore diameter be 1 μm or more and 20 μm or less.
4. the metal component according to claim 1 with overlay film, wherein the 1st deposited metal with a thickness of 20 μm or more
And 400 μm or less.
5. the metal component according to claim 1 with overlay film, wherein the 2nd deposited metal with a thickness of 10 μm or more
And 400 μm or less.
6. the metal component according to claim 1 with overlay film, wherein ground on the surface of the 2nd deposited metal.
7. the metal component according to claim 6 with overlay film, wherein the surface roughness Ra of the 2nd deposited metal is
100nm or less.
8. the metal component according to claim 6 with overlay film, wherein the glossiness on the surface is 75 or more.
9. the metal component according to claim 1 with overlay film, wherein the metal oxide is aluminium oxide.
10. the metal component according to claim 9 with overlay film, wherein in the 1st deposited metal,
The diffracted intensity in (113) face in the X-ray diffraction analysis of the 1st deposited metal, from Alpha-alumina is set as I α, is come from
When the diffracted intensity in (400) face of gama-alumina is set as I γ, by following formula (1):
P α 1 (%)=I α/× 100 ... (1) (I α+I γ)
Defined Alpha-alumina one after another P α 1 is 8% or more and 25% or less.
11. the metal component according to claim 9 with overlay film, wherein in the 2nd deposited metal,
The diffracted intensity in (113) face in the X-ray diffraction analysis of the 2nd deposited metal, from Alpha-alumina is set as I α, is come from
When the diffracted intensity in (400) face of gama-alumina is set as I γ, by following formula (2):
P α 2 (%)=I α/× 100 ... (2) (I α+I γ)
Defined Alpha-alumina one after another P α 2 is 7% or less.
12. the metal component according to claim 10 with overlay film, wherein in the 2nd deposited metal,
The diffracted intensity in (113) face in the X-ray diffraction analysis of the 2nd deposited metal, from Alpha-alumina is set as I α, is come from
When the diffracted intensity in (400) face of gama-alumina is set as I γ, by following formula (2):
P α 2 (%)=I α/× 100 ... (2) (I α+I γ)
Defined Alpha-alumina one after another P α 2 is 7% or less.
13. the metal component according to claim 1 with overlay film, wherein the metal base is aluminium or its alloy.
14. the metal component according to claim 1 with overlay film, wherein the metal base with a thickness of 5mm or less.
15. the metal component according to claim 1 with overlay film, wherein the metal base has carried out surface roughening,
The metal base is integrated by mechanical structure with the sputtered films of bismuth.
16. the metal component according to claim 1 with overlay film, wherein the sputtered films of bismuth is close to the metal base
Conjunction intensity is 5MPa or more.
17. the metal component according to claim 1 with overlay film is the outer exterior material of electric product.
18. a kind of have using the metal component described in any one of claim 1~17 with overlay film as at least outer exterior material
A part article.
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| JP7284553B2 (en) * | 2017-09-21 | 2023-05-31 | 日本特殊陶業株式会社 | Substrate with thermal spray coating and method for manufacturing the same |
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