CN101722141A - Method for forming inorganic film - Google Patents
Method for forming inorganic film Download PDFInfo
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- CN101722141A CN101722141A CN200910208273A CN200910208273A CN101722141A CN 101722141 A CN101722141 A CN 101722141A CN 200910208273 A CN200910208273 A CN 200910208273A CN 200910208273 A CN200910208273 A CN 200910208273A CN 101722141 A CN101722141 A CN 101722141A
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Abstract
The present invention provides a method for forming an inorganic film which has excellent durability without wax or polymer processing. The settlement solution is described as follows: one or more than two ores selected from quartz porphyry, calcium carbide and medical stone which can release silicon component and aluminum component through contacting with water so that the particles of the ceramic material which has a chemical composition of 50-80% by weight of silicon, 10-50% by weight of aluminum, 1.0-10% of titanium and 1.0-9.0% by weight of iron, or the particles with a surface layer with the ceramic material as the base layer component contact with raw water (a), so that the chemical components with charges and the excitation current are dissolved into the raw water for forming charge water (b). Then, after the charge water (b) is introduced and passes through an electromagnetic field so an induced current is generated, the charge water (b) which is executed with magnetic field processing is sprayed to the surface of a workpiece (33) or the workpiece (33) is dipped into the charge water (b) for contacting with the charge water. The inorganic film which takes the oxide of the dissolved component as main component is formed on the surface of the workpiece (33).
Description
Technical field
The present invention is about the inorganic plated film formation method of constituent material surfaces such as the iron that is used to protect jewelry product such as automobile, rolling stock, boats and ships, airborne vehicle, tame electrical article etc. and glasses, jewellery, aluminium, synthetic resin, glass, rubber, ware and coat side thereof.
Background technology
In the past; the surface of the above-mentioned component parts of outdoor uses such as automobile, rolling stock, boats and ships, airborne vehicle is adhered to dust, coal dust, worm etc. easily; often cleaning; at these apparatus surfaces; usually coat, protect by surface coatings such as paraffin, Polymer Processing; but, scolded to be environomental pollution source because these materials are organic substance highly finished product.
In addition, there is following shortcoming in these diaphragms: be subjected to easily the weathering that ultraviolet ray etc. causes influence, film fade, outward appearance or function reduction such as gloss reduction, in addition and since diaphragm this as soft, be subjected to wound easily, the outward appearance protection is insufficient.Therefore, must repeat paraffin or Polymer Processing continually, also exist the cost material cost and man-hour such problem.Again, the daily necessities that glasses, jewelry product, mirror etc. contact with the people, the problem that exist the surface to be easy to generate stain, the lubricant component that adheres to is difficult to remove etc.
As the method for the such problem of reply, the someone proposes to form with the electro-deposition effect of the electric charge of calcium carbide generation the method (referring to Patent Document 1) of boric acid silicon dioxide film.But the diaphragm that these methods obtain can't be can be regarded as on film durability this point fully.
In addition, the present inventor has proposed the invention (below, be called invention formerly) of new inoranic membrane formation method shown in patent documentation 2 and device thereof.And be that improvement has been carried out so that inoranic membrane is high-quality and stable in the basis, and carried out further raising function development with this technology.
The prior art document
Patent documentation
[patent document 1] Japan Patent spy opens the 2000-192086 communique
No. 3948671 communiques of [patent document 2] Japan Patent
Summary of the invention
The present invention is the invention of carrying out for addressing the above problem, purpose is to provide a kind of inoranic membrane formation method, described inoranic membrane formation method not only has and formerly invents same advantage, promptly, can realize protecting the surface, excellent in te pins of durability of outdoor units such as automobile, rolling stock, boats and ships, airborne vehicle and inoranic membrane cheaply, do not need in the past wax or Polymer Processing, help to suppress to pollute, protect environment etc., and, can also realize following improvement: can make high-quality inoranic membrane stable; Improve surface propertys such as the luminosity luster performance of inoranic membrane, anti-cloud point; The degerming etc. that improves electric charge water is to the security of natural, ecological etc.
The present invention is based on above-mentioned invention formerly, be conceived to be used for solving the specific stripping chemical composition of film formation liquid of above-mentioned problem, particularly, based on such knowledge: when the chemical composition in the stripping composition basic material is particular value, can obtain the film properties of stable and high value.
Can address the above problem by inoranic membrane formation method of the present invention; inoranic membrane formation method of the present invention is characterised in that: can stripping silicon composition and the quartz porphyry of aluminium component by contacting with water to be selected from; calcium carbide; a kind of or ore more than 2 kinds in the medical stone is a material; make that to contain chemical composition be silicon 50～80% (quality %; down together); aluminium 10～50%; titanium 1.0～10%; the particle of the ceramic material of iron 1.0～9.0% or to have with these ceramic materials be that the particle on the top layer of top layer composition contacts with former water; make the above-mentioned chemical composition that has electric charge in described former water, become electric charge water with the excitation current stripping; then; described electric charge water imported and pass through electromagnetic field; after making the generation induced-current; the electric charge water that will carry out handling in magnetic field is ejected into surface of the work or workpiece is impregnated into it is contacted with electric charge water, is the inoranic membrane of principal component in surface of the work formation with the oxide of above-mentioned stripping composition.
Chemical composition among the present invention (quality %) is to be 100% o'clock value with the content that constitutes the formation element beyond the deoxygenation in the element.In the following description,, also be the same unless oxide is had explanation in addition.
The present invention is in order to carry out upgrading to film properties, can be embodied as and in above-mentioned ceramic material, contain silver-colored 0.01～0.5% such mode, and then desirable can be embodied as, and above-mentioned silver is the silver made from extra care or extracting from galena, argentite and/or horn silver.
The formation method of inoranic membrane of the present invention constitutes aforesaid mode, and the inoranic membrane that obtains by the processing water that obtains thus is based on the principle of following characteristics.
The inoranic membrane that is obtained by the present invention is by the particle of above-mentioned ceramic material or to have with these ceramic materials be the SiO that the stripping composition of particle on the top layer of top layer composition constitutes
2-Al
2O
3-TiO
2Be ore (stone) film, contain ferrous oxide (being referred to as FeO) as accessory ingredient, and then, can the addition silver oxide.Can also contain magnesia (MgO), calcium oxide (CaO) etc. as subsidiary composition.These films have the character of the ultra-thin membranous type plating of nanometer level, also have the character that electrochemical reaction is electroplated.
Like this, the inoranic membrane that obtains of inoranic membrane formation method according to the present invention is SiO
2-Al
2O
3-TiO
2, during the FeO film, realized low-cost and excellent durability, do not need in the past wax or Polymer Processing, in addition, can expect that polluter self decomposes useful surfactions such as the photochemical catalyst function of removing, high-luster, hydrophily, anti-cloud point.And then, contain silver oxide (AgO) thus film be endowed degerming and become and be of value to the ecosystem.Like this, the present invention is as solving the inorganic membrane formation device of problem points in the past, and practical value is very big.
Description of drawings
[Fig. 1] is used to illustrate the pattern block diagram of main device of the present invention.
The figure of the relation of [Fig. 2] expression expulsion pressure and thickness.
The figure of the relation of [Fig. 3] expression processing time and thickness.
The figure of the reflectivity of [Fig. 4] expression treated side.
The figure of the coefficient of friction of [Fig. 5] expression treated side.
The figure of the case hardness of [Fig. 6] expression treated side.
Photoelectron analysis (ESCA) result's of [Fig. 7] expression treated side figure.
The figure of the pollution decomposability of [Fig. 8] expression treated side.
The figure of the effect that handle in [Fig. 9] expression magnetic field.
The figure of the ferrous components in [Figure 10] expression electric charge water and the relation of the ferrous components in the ceramic material.
[Figure 11] expression is exposed to the figure that outdoor glossiness changes.
The figure of the relation of [Figure 12] expression Si amount, Al amount and glossiness.
The figure of the variation of the contact angle before and after [Figure 13] expression ultrasonic wave is handled.
The figure of the relation between [Figure 14] expression ultrasonic irradiation and the active oxygen.
Symbol description
The aquatic grooving 11 former water supply port 12 electric charge water conveying ends 13 ceramic particle filling departments 14 ceramic particles 2 magnetic field treatment troughs 21 electric charge water of 1 electric charge are sent into mouthful 22 a magnetic treatment water conveying end 23a S utmost point 23b N utmost points 24 and are passed through the water route
3 films form groove 31 magnetic treatment waters and send into mouthful 32 processing draining conveying ends, 33 workpiece, 34 nozzles
The former water b of a electric charge water c magnetic treatment water d handles draining
The specific embodiment
Below, describe with reference to Fig. 1～8, Fig. 9～13 pair related embodiment of inoranic membrane formation method of the present invention.
At first, Fig. 1 represents the principle of inorganic membrane formation device used in the present invention, its basic comprising is, at least the magnetic field treatment trough 2 that carries out handling in magnetic field by the aquatic grooving 1 of electric charge that generates electric charge water, to electric charge water, the film that makes magnetic treatment water contact, form inoranic membrane with surface of the work form groove 3 and constitute, this point with formerly invent the same.
(the aquatic grooving of electric charge)
The aquatic grooving 1 of electric charge has the former water supply port 11 of former water a such as importing running water or well water and takes out the electric charge water conveying end 12 of the electric charge water b after handling, also has ceramic particle filling department 13, described ceramic particle filling portion 13 is filled with: by innerly contact with water, at least the countless particle that constitutes as the ceramic material of stripping composition of stripping silicon, aluminium, titanium, ferrous components (below, being generically and collectively referred to as this particle is the particle on the top layer of top layer composition with having with these ceramic particles, simply is called ceramic particle 14).
Described ceramic particle 14 can be the SiO with following chemical composition
2-Al
2O
3-TiO
2The summary spheric granules of particle diameter 3～10mm that series ceramic material constitutes, in order to improve the formation efficiency of aftermentioned electric charge water, preferably constituted by the ceramic material of material with the ore more than a kind or 2 kinds that is selected from quartz porphyry, calcium carbide, the medical stone that contains more than 50%.Described ceramic material importantly contains silicon 50～80% (quality %, down together), aluminium 10～50%, titanium 1.0～10%, iron 1.0～9.0% as chemical composition (being scaled oxide), exceeds this scope, can not form desirable inoranic membrane.
Above-mentioned quartz porphyry, calcium carbide, medical stone are natural crystals, and its kind has a lot, describes representational.
At first, quartz porphyry has and mineral formation like the granite of volcanic rock, based on quartzy, feldspar, contains the accessory ingredients such as biotite about 10%, and an example of its chemical composition is: SiO
2: Al 77%,
2O
3: 13%, NaKO:8%, contain TiO below 1% in addition
2, Fe
2O
3, MgO etc.
Again, calcium carbide (tourmaline) is by chemical general formula (Ca/Na) (Mg/Fe
2+/ Fe
3+/ Al/Li)
3Al
6(BO
3)
3(Si
6O
18) (OH, F)
4Expression, (Mg/Fe
2+/ Fe
3+When/ special component in Al/Li) was principal component, for example, Mg was called " magnesia calcium carbide ", Fe and is called " ferroelectric stone " when being main when being main.Medical stone is the product of granite weathering, and therefore, an example of its chemical composition is: SiO
2: Al 66%,
2O
3: 16%, NaKO:6%, contain Fe in addition
2O
3: 2%, CaO:3%, MgO:1% etc.
Ceramic material of the present invention and ceramic particle can be made in the following order.
The ore that is selected from quartz porphyry, calcium carbide, medical stone being pulverized mince for making mineral powder below the particle diameter 0.1mm, with its damping, is suitable three-dimensional shapes such as sphere, column type about particle diameter 3～10mm with the comminutor granulation.After granulation thing drying, use the heating furnace sintering.The degree of sintering can be that pack in the operation of aquatic grooving 1 grade of above-mentioned electric charge not can damaged such degree, makes more preferably that to keep water absorption rate be porous matter more than 5%.
Described ceramic particle can be only to be made of the ore that is selected from quartz porphyry, calcium carbide, medical stone, also can add suitable shaping additive (clay class), extender (silica sand, chamotte sand (シ ヤ モ Star ト) etc.), sintering binder (feldspar, glass dust etc.) in above-mentioned ore.Under such situation, in order positively to bring into play action effect of the present invention, importantly selecteed above-mentioned ore accounts for more than 50%.In addition, importantly the chemical composition of these ceramic particles (being scaled oxide) contains silicon 50～80% (quality %, down together), aluminium 10～50%, titanium 1.0～10%, iron 1.0～9.0%.
Can not constitute from the ore that is selected from above-mentioned quartz porphyry, calcium carbide, medical stone under the situation of above-mentioned chemical composition,, be necessary other interpolation for the composition of deficiency.Usually, titanium 1.0～10%, iron 1.0～9.0% can not fully obtain from the ore of selecting, and therefore, by before pulverizing these ores or after pulverizing, add the titanium oxide or the form of iron oxide of mixing requirement, obtain the target chemical composition.
And then, the preferred gimmick as the adding method of titanium, ferrous components is described.
Make before the sintering or sintering after porous matter ore granulated pellet contain the aqueous solution that is immersed in soluble titanium, soluble iron, for example in the aqueous solution of suitable concentration such as Titanium Nitrate, ferric nitrate, add thermal decomposition, can make fine titanium, ferriferous oxide expose, disperse, keep in towards middle body from pore from the surface of granulated pellet.By such gimmick, most addition to be can disperseing with the water state of contact, therefore, is easy to stripping than the situation of simple mixing titanium oxide or iron oxide, can be beneficial to the upgrading based on the film properties of each composition effectively.
Again, in order to obtain the ceramic particle of fixed chemical composition of the present invention, also can prepare the element-specific in the chemical composition of making of suitable kind in advance, for example the content of silicon, aluminium, titanium, iron etc. changes and the ceramic particle of sintering, and combined hybrid is so that they become specific chemical composition.Have the ceramic particle 1～3 of example of the composition of such mixing, be shown in following table 1.By such method, can easily the chemical composition for practical ceramic particle be set in the scope of hope.
Table 1 is supplied to the chemical composition (weight %) of mixing the ceramic particle that uses
| Constitute element | Pottery 1 | Pottery 2 | Pottery 3 |
| ??Na | ??0.51 | ??3.13 | ??9.16 |
| ??Mg | ??- | ??0.44 | ??1.16 |
| ??Al | ??28.41 | ??13.46 | ??22.22 |
| ??Si | ??60.01 | ??70.18 | ??38.59 |
| ??P | ??- | ??- | ??10.93 |
| ??K | ??4.48 | ??5.92 | ??0.62 |
| ??Ca | ??- | ??1.72 | ??0.01 |
| ??Ti | ??5.19 | ??- | ??- |
| ??Fe | ??1.40 | ??5.15 | ??9.87 |
| ??Zr | ??- | ??- | ??7.44 |
| Constitute element | Pottery 1 | Pottery 2 | Pottery 3 |
| (total) | ??(100％) | ??(100％) | ??(100％) |
Ceramic particle of the present invention also can be embodied as, and is the particle of top layer part with the ceramic material with above-mentioned particular chemical composition, that is, and and the particle of the sandwich construction that the top layer is different with the core composition.At this moment, because the stripping composition is by the supply of top layer part, so have the advantage that can reduce the cost of raw material.Self-evident, the top layer part contains the ore of above-mentioned selection more than 50%, and requires to have above-mentioned chemical composition.
Again, the present invention for to the film properties upgrading, pay the degerming performance, preferred contain silver at the surface portion of above-mentioned ceramic particle at least.At this moment, silver contain quantity not sufficient 0.1%, DeGrain surpasses 0.5%, effect can not rise along with content ratio yet, therefore, content is that 0.1～0.5% it is enough.
Again, described silver-colored composition also can be a hybrid metal silver in the ore of selecting, it is desirable to as the situation of above-mentioned titanium, iron, make before the sintering or sintering after granulated pellet contain and be immersed in silver salt solution, for example, in the aqueous solution of suitable concentrations such as silver nitrate, silver chlorate, silver acetate, heating, the words of decomposing, to core, can make fine silver oxide in pore, expose, disperse, keep from the surface of ceramic particle.Like this, the silver of dispersion can not covered by other compositions, and all additions can stripping, therefore can be beneficial to the upgrading of above-mentioned film properties with less silver content effectively.
Again, by such method, have can the simple adjustment silver content advantage.Silver content and the proportional relation of impregnation measurer as the ceramic particle silver salt solution of object again, with the also proportional relation of the concentration of silver salt solution, therefore, by the concentration or the impregnation amount of control silver salt solution, can be adjusted the silver content of ceramic particle.
Preferred above-mentioned silver is the silver made from extra care or extracting from galena, argentite and/or horn silver.
The state that these ceramic particles can pass through when contacting with this ceramic particle 14 with the former water a that sends into from former water supply port 11 is loaded in the ceramic particle filling department 13.Preference as, by the current of former water a, ceramic particle 14 is flowed to be stirred, ceramic particle 14 fully contacts with former water a, therefore, under such situation, ceramic particle can flow and be loaded, and is better like this.
In the aquatic grooving 1 of described electric charge, former water a and the ceramic particle 14 contacted words that contain above-mentioned composition of ores, moment is at discharge in water, with the excitation current while, at least stripping composition stripping from ceramic particle 14 of silicon, aluminium, titanium, iron obtains the electric charge water b of activate with charged state stripping.Described excitation current can from described ceramic particle 14 semipermanents obtain, therefore, become the inorganic film formed main starting power that obtains by the present invention.
(magnetic field treatment trough)
Magnetic field treatment trough 2 has the magnetic treatment water conveying end 22 that the electric charge water of sending into the electric charge water b that obtains in the aquatic grooving 1 of above-mentioned electric charge is sent into mouth 21 and taken out magnetic treatment water c, dispose inner S utmost point 23a and the N utmost point 23b that forms electromagnetic field, what be provided with electric charge water b therebetween passes through water route 24, constitutes thus.
In described magnetic field treatment trough 2, charged above-mentioned electric charge water b is imported in the electromagnetic field that is formed by S utmost point 23a and N utmost point 23b, flow through by water route 24, by faraday's rule produce fixed induced-current, electric charge water b is removed as the magnetic treatment water c of activate more.In the purpose that handle in described magnetic field, preferably the intensity with electromagnetic field is set at 0.10～0.80mG, more preferably is set at 0.30～0.80mG.Such condition with formerly invent just the same.
At this moment, even not carrying out magnetic field handles, by above-mentioned electric charge water, also can obtain inoranic membrane to a certain degree, but, carried out magnetic field and handled, particularly on the points such as durability of film formed stability, formation film, can obtain result preferably, therefore, the magnetic field treatment trough is not omissible important device among the present invention.
(film formation groove)
Film of the present invention forms groove 3 and has the processing draining conveying end 32 that the magnetic treatment water of sending into the magnetic treatment water c that obtains in the above-mentioned magnetic field treatment trough 2 is sent into mouth 31 and taken out processing draining d, as the means that the surface of the workpiece 33 in making magnetic treatment water c and being configured in groove contacts, has nozzle 34 in the example of Fig. 1 to the magnetic treatment water c of the jet surface pressurization of workpiece 33.
Form in the groove 3 at described film, contact with workpiece 33 surfaces by magnetic treatment water c, each stripping composition of the silicon at least among the magnetic treatment water c, aluminium, titanium, magnesium, iron, the electrochemical reaction based on cathodic reduction is separated out forms inoranic membrane on the surface of workpiece 33.The result of photoelectric analysis (ESCA) shows that described inoranic membrane is a principal component with the oxide of stripping composition silicon, aluminium, titanium, magnesium, iron, is the SiO of oxide bonding separately
2-Al
2O
3-TiO
2, MgO, FeO the system hyaloid.
In such film forming, also be feasible certainly, but preferably use the whole surface that the magnetic treatment water c of pressurization is ejected into workpiece 33 with nozzle shown in Figure 1 such as the method that workpiece 33 is immersed among the magnetic treatment water c.Reason is to spray from nozzle 34 to impact, and produces dash current, can improve film forming efficiency.
Among the present invention, the summation of preferred above-mentioned excitation current, induced-current, dash current remains on 0.05～0.07mA.Reason is positively to form the inoranic membrane of excellent in te pins of durability described later.
Then, the part with the characteristic of inoranic membrane of the present invention is shown in Fig. 2～9 and Figure 10.These characteristics do not have substantial difference with invention formerly.
That is, by the relation between the thickness of above-mentioned expulsion pressure shown in Figure 2 and the film that obtains, as can be seen, at 10～500N/cm
2Pressure limit in, thickness is roughly stable in the scope of 10～60nm, and (a plurality of zero symbolic representations among the figure change the situation of film formation conditions.Fig. 3 also is same).
Form the processing time of groove 3 and the relation of the thickness that obtains according to film shown in Figure 3, even it is before and after 1 second of moment, also can obtain the film of thickness 10～100nm,, preferred more than 10 seconds in order to obtain the stable film of 10～60nm, uneconomical more than 60 seconds, therefore do not need.Again, when above-mentioned electric charge water was supplied to above-mentioned film forming, the temperature that preferred film of the present invention forms the treatment fluid in the groove 3 remained on 30～50 ℃.
And then; Fig. 4 about show the film surface coarse, fade or the specular reflectivity of gloss deterioration index; even with 1 treated side of the present invention (symbol f), 2 treated sides (symbol g), 5 treated sides (symbol h) respectively with wax treated side (symbol e; each following figure is too) to compare, film of the present invention is also bigger to the protection effect of quality coating surface.
Again; Fig. 5 adheres to the coefficient of friction (dynamic friction) of the index of difficulty and cleaning easness about the dust or the stained thing of coating surface; hence one can see that; the same with Fig. 4; Fig. 5 is the figure of treated side more of the present invention and wax treated side; can find out also that thus film of the present invention, the thing of its dust etc. adhere to difficulty and the cleaning easness is all very excellent.
And then, Fig. 6 shows is the figure of the case hardness represented with pencil hardness, case hardness equally also is the index of coating surface durability, Fig. 6 shows and the above-mentioned same figure that carries out treated side result relatively, can see significant difference in this, excellent too on durability.
Again, Fig. 7 is photoelectric analysis (ESCA) result of the inoranic membrane of stripping composition when being silicon, aluminium, titanium, and hence one can see that, and the oxide that has formed with each stripping composition of silicon, aluminium, titanium is the SiO that principal component, oxide bonding separately form
2-A1
2O
3-TiO
2Be the rete of the depth capacity of hyaloid for the NM level of about 80nm.Among Fig. 7, zero expression is represented photoelectricity number/second based on Ti based on photoelectricity number/second, the △ of Si.Film when not containing Ti is shown ●.
Fig. 8 carries out film forming of the present invention on the white glass plate, coating prepared Chinese ink liquid is exposed to outdoorly as polluter on it, represents the situation that it fades with transparency (transparent fully=100, opaque=0), and zero represents situation of the present invention, and △ represents SiO
2-Al
2O
3The situation of mesentery, represents to be coated with the situation of titania photocatalyst, the situation of * expression non-processor.Hence one can see that, and (zero) has the resolution characteristic that can be equal to mutually with titania photocatalyst () under the situation of the present invention.
Fig. 9 represents the effect that handle in magnetic field, and whether expression magnetic field handles influential to the typical thickness that forms film.Irrelevant with expulsion pressure, when carrying out the magnetic field processing, the thickness of film can be thickeied about 2 times.
Then, Figure 10 shows the ferrous components in the ceramic particle and the relation of the ferrous components in the electric charge water.
Can confirm thus, be present in ferrous components in the electric charge water in the content tolerance band (below the 0.3mg/l) of heavy metal, have 0.01～0.3mg/l, be suitable and effective amount as common mineralogical composition.Like this, 1～9% the ferrous components rich ore materialization to bioecosystem in the formation of film that contains in the ceramic material is very effective.
Then, surfaction (glossiness, hydrophily, anti-cloud point, the degerming etc.) situation of the inoranic membrane of realizing by the present invention with reference to Figure 11～14, table 1 pair describes.
Here, the chemical composition of the ore that ceramic particle is selected is divided into following 2 kinds: the high Si-Al-Ti system that is equivalent to embodiment: the film of silicon 50～80%, aluminium 10～50%, titanium 1～10%, iron 1～9% o'clock (among each figure with zero expression), with the low Si-Al-Ti that is equivalent to comparative example be: the film when silicon less than 50%, aluminium less than 20%, titanium less than 1% (with zero expression of band stain) compares each film.As a reference, the wax processing list is shown, and polymer coating is expressed as △.
Figure 11 use be exposed to outdoor during corresponding glossiness change the quality of representing film, under the situation of embodiment, worsen minimum, exterior durability is also excellent.Again, Figure 12 represents the influence of the composition of silicon, aluminium to glossiness (the numeric representation glossiness % among the figure), and embodiment demonstrates the film of glossiness of the situation excellence of the low Si-Al-Ti system (low silicon, low aluminium) that can obtain than comparative example.
The contact angle of the rinse water of automobile body application face (2 θ), embodiment are that 13 °, comparative example are that 18 °, wax treated side are 40 °, and the embodiment hydrophily is the highest.And then Figure 13 represents that the hydrophily of embodiment and comparative example changes, even ultrasonic irradiation produces the situation of active oxygen, the reduction trend of contact angle also is that embodiment is the most obvious, shows the hydrophily excellence.
Figure 14 is about the anti-cloud point of film, and as can be known, embodiment produces more active oxygen than comparative example.Described active oxygen helps to improve the hydrophily on film surface as previously mentioned, therefore, can obtain to prevent the effect (anti-cloud point) of cloud point.
At this moment, ultrasonic irradiation and composition effect of the present invention are irrelevant, and what show is to have multiplier effect with ultrasonic irradiation.
Then, the degerming with embodiment is shown in table 2.This is the summary of the experimental result of carrying out in Tokyo food technology research institute, the common drinking water that connects with each symphysis through after 24 hours, the situation of change of the harmful bacterium of investigation, under the situation of general polymer container, coliform significantly breeds, staphylococcus shades and the container of the film of embodiment can prove to have significantly bacteria-eliminating efficacy.When especially containing silver, bacteria-eliminating efficacy is remarkable.
Table 2
Register procuratorial organs by health work minister processing water of the present invention is carried out examination of water, obtain following result.General bacterium: 0, coliform: do not detect, heavy metal (cadmium, mercury, lead, arsenic, 6 valency chromium, zinc, iron, copper, manganese): benchmark below 0.1, other (cyano group, nitrate nitrogen, fluorine, chlorions etc.): benchmark meets the water quality benchmark of food hygiene law below 0.1.
The inoranic membrane that obtains according to the present invention, as mentioned above, compare, given play to excellent performance with wax or similar Polymer Processing, and, as mentioned above, inoranic membrane formation method of the present invention needs running stores hardly, and operation power is also very little, therefore the operating cost of device is considerably less, it is also easy to safeguard, therefore, is the very excellent method of economy.And then, be expected can make helps to preventing public hazards, improve environment, suppress global warming etc., contribute.
In the processing object of the present invention, can be object with many kinds parts such as the iron of the component parts that is used for automobile, rolling stock, boats and ships, airborne vehicle, tame electrical article etc., aluminium, synthetic resin, glass, rubber.The surface texture of these workpiece can be any one of the material coated face that exposes face and cold coating etc., can be suitable for without barrier, but from the viewpoint on guard block surface, preferably is object with the coated face.
Claims (3)
1. inoranic membrane formation method; it is characterized in that; can stripping silicon composition and the quartz porphyry of aluminium component to be selected from by contacting with water; calcium carbide; a kind of or ore more than 2 kinds in the medical stone is a material; make that to contain chemical composition be silicon 50～80% (quality %; down together); aluminium 10～50%; titanium 1.0～10%; the particle of the ceramic material of iron 1.0～9.0% or to have with these ceramic materials be that the particle on the top layer of top layer composition contacts with former water; make the above-mentioned chemical composition that has electric charge in described former water, become electric charge water with the excitation current stripping; then; with described electric charge water importing and by in the electromagnetic field; after making the generation induced-current; the electric charge water that will carry out handling in magnetic field is ejected into surface of the work or workpiece is impregnated into it is contacted with electric charge water, is the inoranic membrane of principal component in surface of the work formation with the oxide of above-mentioned stripping composition.
2. inoranic membrane formation method according to claim 1 is characterized in that above-mentioned ceramic material contains 0.01～0.5% silver.
3. inoranic membrane formation method according to claim 2 is characterized in that, above-mentioned silver is the silver made from extra care or extracting from galena, argentite and/or horn silver.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008271821 | 2008-10-22 | ||
| JP2008-271821 | 2008-10-22 | ||
| JP2009226204A JP2010120010A (en) | 2008-10-22 | 2009-09-30 | Method for forming inorganic coating film |
| JP2009-226204 | 2009-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101722141A true CN101722141A (en) | 2010-06-09 |
Family
ID=42321818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910208273A Pending CN101722141A (en) | 2008-10-22 | 2009-10-22 | Method for forming inorganic film |
Country Status (2)
| Country | Link |
|---|---|
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| CN (1) | CN101722141A (en) |
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| CN2786146Y (en) * | 2004-07-16 | 2006-06-07 | 姜培齐 | Surface anti-bacterial and wearable product |
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| CN2786146Y (en) * | 2004-07-16 | 2006-06-07 | 姜培齐 | Surface anti-bacterial and wearable product |
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