CN100344796C - Molten salt bath for electroforming and method of manufacturing metal product using the same - Google Patents
Molten salt bath for electroforming and method of manufacturing metal product using the same Download PDFInfo
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- CN100344796C CN100344796C CNB2004100050435A CN200410005043A CN100344796C CN 100344796 C CN100344796 C CN 100344796C CN B2004100050435 A CNB2004100050435 A CN B2004100050435A CN 200410005043 A CN200410005043 A CN 200410005043A CN 100344796 C CN100344796 C CN 100344796C
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/66—Electroplating: Baths therefor from melts
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
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Abstract
The molten salt bath for electroforming comprises lithium bromide, cesium bromide, a halide of alkali metal and/or a halide of alkaline-earth metal. Further, the molten salt bath for electroforming is obtained by mixing lithium bromide, cesium bromide, the halide of alkali metal and/or the halide of alkaline-earth metal. The method of producing a metallic product comprises: a stage where a resist pattern is formed on an electrically conductive substrate to expose a part of the electrically conductive substrate; a stage where the electrically conductive substrate with the resist pattern formed is dipped into the molten salt bath for electroforming admixed with the metal to be precipitated and/or the compound of the metal to be precipitated; and a stage where the metal is precipitated over the part to which the electrically conductive substrate is exposed.
Description
Technical field
The present invention relates to a kind of electroforming molten salt bath and use it to prepare the method for metal products, more specifically, the present invention relates to a kind of permission at low temperatures electroforming the electroforming molten salt bath and use it to prepare the method for metal products.
Background technology
Conventionally, the LiCl-KCl base eutectic mixture that obtains by mixed chlorinated lithium (LiCl) and Repone K (KCl) is often used as the electroforming molten salt bath.
For example, with the tungsten chloride (WCl of 0.1～10 quality % of electroforming molten salt bath total mass
2) be added in the electroforming molten salt bath, described electroforming molten salt bath is by being mixed with respect to the LiCl of 45 quality % of electroforming molten salt bath total mass and the KCl of 55 quality %.Then, will be immersed in by the pair of electrodes that anode and negative electrode are formed in the electroforming molten salt bath, thereafter, under argon gas (Ar) atmosphere, under about 500 ℃ heated condition, between these electrodes, supply with several A/dm
2Electric current.So, tungsten (W) is deposited in cathode surface, forms the metal products with regulation shape by this.
On the other hand, LiCl-KCl base electroforming molten salt bath has about 352 ℃ high-melting-point, therefore, have to carry out electroforming in the temperature higher than this temperature, for example, at aforesaid approximately 500 ℃.If use and have the electroformed mould (electroforming mold) of resist pattern (resist pattern) as negative electrode, basically the resist pyrolysis of forming by acrylic acid or the like (acrylic), can not obtain to stipulate the metal products of shape, wherein said resist pattern is to be formed on the surfaces of conductive substrates of being made by stainless steel etc.
So, for the molten salt bath of the electroforming molten salt bath of needs pyritous such as LiCl-KCl base, can use the electroformed mould that obtains by silicon (Si) groove etched (trench etching) or the electroformed mould that obtains by glass bat printing (glass transfer) as negative electrode.
With reference to figure 4A～4D, the method for utilizing silicon groove etching to prepare electroformed mould will be described now.Should be noted that in the accompanying drawings identical reference marker (reference character) is represented identical or corresponding parts all the time.
At first, as shown in Fig. 4 A, nickel (Ni) film 11 is formed on the Si base material 10, then, utilizes to electroplate further Ni to be deposited on the Ni film 11, increase the thickness of Ni film 11 with this, as shown in Fig. 4 B by sputter.After this, as shown in Fig. 4 C, Si base material 10 is subjected to groove etched, makes Si base material 10 form the shape of regulation with this.At last, as shown in Fig. 4 D, with metallic membrane 12 hydatogenesiss on the surface of Ni film 11 that exposes and Si base material 10.Like this, by utilizing the groove etched electroformed mould that prepared of Si.
With reference to figure 5A～5D, the method for utilizing the glass bat printing to prepare electroformed mould will be described now.At first, as shown in Fig. 5 A, utilize to use the SR lithography of synchrotron radiation (synchtron radiation) light, make resist 19 on the conductive base of making by stainless steel etc. 1, form pattern.Then, as shown in Fig. 5 B, utilize the shape of electroplating the chair regulation that Ni film 11 is formed on the conductive base 1.After this, as shown in Fig. 5 C, remove resist 19, Ni film 11 is separated from conductive base 1.At last, as shown in Fig. 5 D, the shape of Ni film 11 is transferred on the glass 14, thereafter, with the surface of metallic membrane 12 hydatogenesiss at glass 14.So, by utilizing the glass bat printing to prepare electroformed mould.
Yet, in the electroformed mould that utilizes the groove etched acquisition of Si, formed by the groove etched bar paten that causes (strip pattern).Therefore, similarly bar paten also is formed on by on the surface that utilizes the metal products that electroformed mould obtains.
In addition, in the electroformed mould that utilizes the glass bat printing to obtain, the precipitated metal of electroformed mould surface becomes coarse owing to repetitive displacement repeatedly.Therefore, has inferior tolerance range by the metal products that uses electroformed mould to obtain.
And, in the aforesaid electroformed mould of preparation, need a large amount of operations, therefore, the preparation electroformed mould is expensive.
Summary of the invention
Consider the problems referred to above, an object of the present invention is to provide a kind of permission at low temperatures electroforming the electroforming molten salt bath and use it to prepare the method for metal products.
According to the present invention, provide a kind of lithiumbromide that contains, cesium bromide, and the halid electroforming molten salt bath of alkali-metal halogenide and/or alkaline-earth metal.It is believed that the material that is contained among the electroforming molten salt bath of the present invention is Ionized at least partially in the electroforming molten salt bath here.
In electroforming molten salt bath of the present invention, the halogenide of preferred as alkali is Potassium Bromide.
In addition, in electroforming molten salt bath of the present invention, with respect to whole molten salt baths, the molar fraction of preferred lithiumbromide and the molar fraction sum of cesium bromide are set at least in 0.5 arrives less than 0.95 scope.
In addition, in electroforming molten salt bath of the present invention, the mol ratio (lithiumbromide/cesium bromide) of preferred lithiumbromide and cesium bromide is set at least 1.8 and arrives at the most in 2.5 the scope.
Preferred electroforming molten salt bath of the present invention has the eutectic component.
In addition, according to the present invention, provide a kind of method for preparing metal products, it may further comprise the steps: a part that forms the resist pattern and the conductive base that exposes on conductive base; The conductive base that will have the resist pattern of formation is immersed in the above-mentioned electroforming molten salt bath, and this electroforming molten salt bath contains the compound that is about to precipitated metal and/or is about to precipitated metal; And at the partly precipitated metal of conductive base exposure.
In the method for preparing metal products of the present invention, when the precipitation metal, the temperature of preferred electroforming molten salt bath is set at 300 ℃ at the most.
Further according to the present invention, the electroforming molten salt bath is by the mixing lithiumbromide, cesium bromide, and the halogenide of alkali-metal halogenide and/or alkaline-earth metal obtains.
Together with accompanying drawing, from the following detailed description of the present invention, aforementioned and other the purpose of the present invention, characteristics, aspect and advantage will become more obvious.
Description of drawings
Figure 1A～1C is the schematic transverse section figure that is used for the present invention's conductive base.
Fig. 2 is perspective side figure, schematically shows an example of the electroforming apparatus that is used for the present invention.
Fig. 3 is the schematic perspective side elevational view that is used for the experimental installation of embodiment.
Fig. 4 A～4D is schematic transverse section figure, shows the flow process when using the groove etched preparation electroformed mould of conventional Si.
Fig. 5 A～5D is schematic transverse section figure, shows the flow process when using conventional glass bat printing to prepare electroformed mould.
Specific embodiments
The electroforming molten salt bath
According to the present invention, provide a kind of lithiumbromide (LiBr) that contains, cesium bromide (CsBr), and the halid electroforming molten salt bath of alkali-metal halogenide and/or alkaline-earth metal.With replacing the bromide mixing of the LiCl-KCl base material of muriate such as routine to have larger sized negatively charged ion, also comprise positively charged ion (Li here, with different size so that the electroforming molten salt bath has both comprised
+, Cs
+), reduce negatively charged ion and cationic avidity by this.In addition, by mixing three kinds or more kinds of halogenide, reduced the fusing point of the fused salt that comprises the electroforming molten salt bath.From a kind of like this technological concept, finished the electroforming molten salt bath that allows electroforming at low temperatures.Allow electroforming under lower temperature though supposed the electroforming molten salt bath of being made up of halogenide basically, molten salt bath has become unstable and can not carry out actual electroforming.
When using the electroforming molten salt bath, can carry out electroforming at low temperatures, for example, at least 230 ℃ in 300 ℃ scope at the most.Therefore, can not carry out electroforming under the pyrolytic temperature at resist.So the electroformed mould that replaces the complicated procedures of forming by routine to obtain has used the electroformed mould that only has resist pattern, i.e. preparation easily, prepare by having high-melting-point and high-intensity metal such as chromium (Cr), tungsten (W), the metal products that titanium (Ti) constitutes with pinpoint accuracy ground.
By fusing and mixing LiBr powder, the CsBr powder, and the halogenide powder of alkali-metal halogenide powder and/or alkaline-earth metal can obtain the electroforming molten salt bath.Should be pointed out that electroforming molten salt bath of the present invention can contain other the oxide compound of material as producing inevitably.
Except LiBr and CsBr, alkali-metal halid example comprises lithium fluoride (LiF), lithium chloride (LiCl), lithium iodide (LiI), Sodium Fluoride (NaF), sodium-chlor (NaCl), Sodium Bromide (NaBr), sodium iodide (NaI), Potassium monofluoride (KF), Repone K (KCl), Potassium Bromide (KBr), potassiumiodide (KI), rubidium fluoride (RbF), rubidium chloride (RbCl), rubidium bromide (RbCl), rubidium iodide (RbI), cesium fluoride (CsF), cesium chloride (CsCl), or cesium iodide (CsI).
The halid example of alkaline-earth metal comprises magnesium fluoride (MgF
2), magnesium chloride (MgCl
2), magnesium bromide (MgBr
2), magnesium iodide (MgI
2), Calcium Fluoride (Fluorspan) (CaF
2), calcium chloride (CaCl
2), Calcium Bromide (CaBr
2), calcium iodide (CaI
2), strontium fluoride (SrF
2), strontium chloride (SrCl
2), strontium bromide (SrBr
2), strontium iodide (SrI
2), barium fluoride (BaF
2), bariumchloride (BaCl
2), barium bromide (BaBr
2), or barium iodide (BaI
2).
In the middle of other, preferably KBr is mixed as alkali-metal halogenide.In this case, have between Li
+And Cs
+Alkali metal cation (the K of the intermediate sizes between the size
+) can further be contained in the electroforming molten salt bath.Therefore, positively charged ion in the electroforming molten salt bath and the avidity between the negatively charged ion can further reduce.Particularly, when using by mixing LiBr, when CsBr and KBr and the electroforming molten salt bath that obtains, can under further low temperature, carry out electroforming.Only should comprise the halid at least a of alkali-metal halogenide and alkaline-earth metal here.The halogenide that can comprise in addition, one type or two or more types.
With respect to having amount of substance is whole electroforming molten salt baths of 1, and preferably, the molar fraction sum of mixing the molar fraction that makes LiBr and CsBr is set at least 0.5 to less than in 0.95 the scope.If the molar fraction sum, can not reach reduction less than 0.5 fully by comprise the positively charged ion (Li that has larger sized negatively charged ion and have different size in the electroforming molten salt bath
+, Cs
+) negatively charged ion and the effect of the avidity between the positively charged ion.On the other hand, if the molar fraction sum be 0.95 or more than, can not fully reach the effect of fused salt fusing point that reduce to form the electroforming molten salt bath, described electroforming molten salt bath is to obtain by the halogenide that mixes except that LiBr and CsBr.
And, preferably, mix the mol ratio (LiBr/CsBr) that makes LiBr and CsBr and be set at least 1.8 in 2.5 scope at the most.If mol ratio (LiBr/CsBr) is less than 1.8, too many have a larger sized positively charged ion (Cs
+) tend to be present in the electroforming molten salt bath.Therefore, can not reach fully and reduce negatively charged ion and by comprising the effect of the avidity between the cationic positively charged ion with different size.On the other hand, if mol ratio (LiBr/CsBr) surpasses 2.5, the too many positively charged ion (Li with smaller szie
+) tend to be present in the electroforming molten salt bath.Therefore, can not reach fully and reduce negatively charged ion and by comprising the effect of the avidity between the cationic positively charged ion with different size.
In addition, preferably, with LiBr, CsBr, and the halogenide of alkali-metal halogenide and/or alkaline-earth metal mixes so that the electroforming molten salt bath has the eutectic component.In this case, owing to can under eutectoid point, prepare the electroforming molten salt bath, so can near eutectic temperature, carry out electroforming.
From the viewpoint of above-mentioned technological concept, electroforming molten salt bath of the present invention can have three metamembers at least, for example: LiBr-CsBr-KBr, LiBr-CsBr-LiF, LiBr-CsBr-LiCl, LiBr-CsBr-LiI, LiBr-CsBr-NaF, LiBr-CsBr-NaCl, LiBr-CsBr-NaBr, LiBr-CsBr-NaI, LiBr-CsBr-KF, LiBr-CsBr-KCl, LiBr-CsBr-KI, LiBr-CsBr-RbF, LiBr-CsBr-RbCl, LiBr-CsBr-RbBr, LiBr-CsBr-RbI, LiBr-CsBr-CsF, LiBr-CsBr-CsCl, LiBr-CsBr-CsI, LiBr-CsBr-MgF
2, LiBr-CsBr-MgCl
2, LiBr-CsBr-MgBr
2, LiBr-CsBr-MgI
2, LiBr-CsBr-CaF
2, LiBr-CsBr-CaCl
2, LiBr-CsBr-CaBr
2, LiBr-CsBr-CaI
2, LiBr-CsBr-SrF
2, LiBr-CsBr-SrCl
2, LiBr-CsBr-SrBr
2, LiBr-CsBr-SrI
2, LiBr-CsBr-BaF
2, LiBr-CsBr-BaCl
2, LiBr-CsBr-BaBr
2, LiBr-CsBr-BaI
2LiBr-CsBr-KBr-LiF, LiBr-CsBr-KBr-LiCl, LiBr-CsBr-KBr-LiI, LiBr-CsBr-KBr-NaF, LiBr-CsBr-KBr-NaCl, LiBr-CsBr-KBr-NaBr, LiBr-CsBr-KBr-NaI, LiBr-CsBr-KBr-KF, LiBr-CsBr-KBr-KCl, LiBr-CsBr-KBr-KI, LiBr-CsBr-KBr-RbF, LiBr-CsBr-KBr-RbCl, LiBr-CsBr-KBr-RbBr, LiBr-CsBr-KBr-RbI, LiBr-CsBr-KBr-CsF, LiBr-CsBr-KBr-CsCl, LiBr-CsBr-KBr-CsI, LiBr-CsBr-KBr-MgF
2, LiBr-CsBr-KBr-MgCl
2, LiBr-CsBr-KBr-MgBr
2, LiBr-CsBr-KBr-MgI
2, LiBr-CsBr-KBr-CaF
2, LiBr-CsBr-KBr-CaCl
2, LiBr-CsBr-KBr-CaBr
2, LiBr-CsBr-KBr-CaI
2, LiBr-CsBr-KBr-SrF
2, LiBr-CsBr-KBr-SrCl
2, LiBr-CsBr-KBr-SrBr
2, LiBr-CsBr-KBr-SrI
2, LiBr-CsBr-KBr-BaF
2, LiBr-CsBr-KBr-BaCl
2, LiBr-CsBr-KBr-BaBr
2, or LiBr-CsBr-KBr-BaI
2, should be pointed out that symbol such as the LiBr-CsBr-MX in above-mentioned means LiBr, CsBr and MX mix to form electroforming molten salt bath of the present invention.
The method for preparing metal products
Below, with reference to legend the preferred embodiment that the present invention prepares the metal products method will be described.
Copper (Cu), iron (Fe), the conductive base 1 that nickel (Ni) etc. is made at first,, for example, have been prepared by stainless steel with reference to figure 4.Then, with reference to Figure 1B, resist is imposed on the conductive base 1 also with UV (ultraviolet) line or SR photoirradiation.Here, if use UV wire spoke shines resist 2, UV resist etc. just are used as resist 2, and if use the SR photoirradiation, use PMMA (methyl methacrylate) etc. are as resist 2.
Then, with reference to figure 1C, will be except removing on conductive base 1, to form resist pattern with the part the resist 2 of UV line or SR photoirradiation.And the surface of conductive base 1 is the part exposure.Formed electroformed mould 3 like this.In the present invention, the electroformed mould 3 that forms with so simple method can use.
For example, such electroformed mould 3 is placed on as negative electrode in the electroforming apparatus 4 in the schematic perspective side elevational view that is shown in Fig. 2 to carry out electroforming.With reference to figure 2, under argon gas atmosphere, will comprise stainless steel stent (holder) 5, can seal the lid 6 of stainless steel stent 5, anode 7, the crucible of making by rafifinal 8, reference electrode 13, and the electroforming apparatus 4 of thermometric thermopair 15 is put in closed-loop operation case (globebox) (not shown).
To put in the crucible 8 by the electroforming molten salt bath 9 that fusing and mixing LiBr powder and CsBr powder etc. obtain.Here, electroforming molten salt bath 9 comprises with precipitated metal and/or with the compound of precipitated metal in electroformed mould 13.Have high-melting-point and high-intensity metal such as Cr, W or Ti suitable be in the electroformed mould 13 with precipitated metal.If such metal is added in the solution and carries out electroforming, at negative electrode H
2Output greater than metal, because in whole Ph scopes, the reduction potential of this metal is lower than the reduction potential of (baser metal) hydrogen.Therefore, if what apply is sedimentary fully low (benchmark) current potential of the startup of metal, H
2The a large amount of generation, and the utmost point is difficult to the shape precipitation metal of film.Yet, if use electroforming molten salt bath 9 of the present invention, metal such as Cr, W or Ti have the reduction potential that is lower than (baser metal) basic metal and alkaline-earth metal, and therefore, can precipitate such metal on negative electrode.Here, the example with the compound of precipitated metal comprises tungsten chloride (WCl
2), chromium chloride (CrCl
2), titanium chloride (TiCl
2), tungsten bromide (WBr
2), chromic bromide (CrBr
2), tungsten fluoride (WF
2), and chromium fluoride (CrF
2).
Be heated in electroforming molten salt bath 9 and carry out electroforming under about 200～300 ℃ state.Here, if at anode 7 and serve as that the supply current density is not less than 1mA/cm between the electroformed mould 13 of negative electrode
2To being not more than 500mA/cm
2Electric current, preferably be not less than 10mA/cm
2To being not more than 500mA/cm
2, more preferably be not less than 50mA/cm
2To being not more than 500mA/cm
2, above-mentioned precipitated metal forms the metal products with regulation shape by this on the surface of the electroformed mould 13 that serves as negative electrode.
In other words, if supply the electric current of the current density of above-mentioned scope, in the shorter time, can form and have the more metal products of high rigidity.
Finish after the electroforming, from electroforming molten salt bath 9, take out electroformed mould 3 and water flushing.Then, the metal products of being wanted is separated from electroformed mould 3, and remove the resist 2 that is attached on the isolating metal products, for example, utilize ashing.Like this, obtained to have the metal products of the shape of regulation.
As mentioned above, among the present invention, the temperature of electroforming molten salt bath 9 is set to and is not more than 300 ℃ when the precipitation metal.Therefore, even electroformed mould 3 is immersed in the electroforming molten salt bath 9, the resist 2 that is formed on the electroformed mould 3 can pyrolysis yet.Owing to can use the electroformed mould 3 that only has the resist 2 that is formed on the conductive base 1, the metal products that can have pinpoint accuracy with lower cost acquisition.
Use
Electroforming molten salt bath of the present invention and use its method for preparing metal products to have above-mentioned advantage.Therefore, this electroforming molten salt bath and this method are suitable is not less than 600 to the metal products (for example, metal pattern) that is not more than 2000 as preparation Vickers' hardness (HV).
Embodiment
In the crucible in the experimental installation 18 in being shown in the schematic perspective side elevational view of Fig. 3, prepared the electroforming molten salt bath 9 among the embodiment 1～9 with the composition that is shown in Table 1.Then, with CrCl
2Be added in each electroforming molten salt bath with following amount: with respect to whole electroforming molten salt baths, its molar fraction reaches 0.01.Thereafter, the temperature of each electroforming molten salt bath among the embodiment 1～9 is being set under the state of 250 ℃ or 300 ℃, 10 minutes 10mA/cm of supply between (Cr plate) 17 of the Cr pole plate in experimental installation 18 and the nickel pole plate (Ni plate) 16
2, 50mA/cm
2Or 100mA/cm
2Electric current.Based on following standard, with the state of estimating or be deposited in the Cr on the nickel pole plate with the optics microscopic evaluation.Evaluation result is shown in Table 1.Notice that this experiment is under argon gas atmosphere, operates in the closed-loop operation case.
Table 1
| Component | Ratio of component | Cr precipitates state | ||||||||||
| 250℃ | 300 | |||||||||||
| 1 | 2 | 3 | 1∶2∶3 | The 1+2/ | 1/2 | 10 (mA/cm 2) | 50 (mA/cm 2) | 100 (mA/cm 2) | 10 (mA/cm 2) | 50 (mA/cm 2) | 100 (mA/cm 2) | |
| | LiBr | CsBr | KBr | 31.1∶13.9∶55.0 | 0.45 | 2.24 | C | C | C | B | | C |
| Embodiment | ||||||||||||
| 2 | LiBr | CsBr | KBr | 34.6∶15.4∶50.0 | 0.50 | 2.24 | B | B | B | B | | B |
| Embodiment | ||||||||||||
| 3 | LiBr | CsBr | KBr | 56.1∶25.0∶18.9 | 0.811 | 2.24 | A | A | A | A | A | A |
| Embodiment 4 | LiBr | CsBr | KBr | 65.7∶29.2∶5.1 | 0.949 | 2.24 | B | B | B | B | B | B |
| Embodiment 5 | LiBr | CsBr | KBr | 67.1∶29.9∶3.0 | 0.97 | 2.24 | C | C | C | C | C | C |
| Embodiment 6 | LiBr | CsBr | KBr | 49.9∶31.2∶18.9 | 0.811 | 1.6 | B | B | C | B | B | C |
| Embodiment 7 | LiBr | CsBr | KBr | 52.1∶29.0∶18.9 | 0.811 | 1.8 | B | B | B | B | B | B |
| Embodiment 8 | LiBr | CsBr | KBr | 57.9∶23.2∶18.9 | 0.811 | 2.5 | B | B | B | B | B | B |
| Embodiment 9 | LiBr | CsBr | KBr | 59.2∶21.9∶18.9 | 0.811 | 2.7 | B | B | C | B | B | C |
Judgement criteria
A... fabulous precipitation also observes metal cluster.
B... good precipitation also observes metal cluster.
C... observe precipitation, yet smoothness is abundant inadequately.Do not observe metal cluster.
D... almost do not observe precipitation.
So, as shown in table 1, with respect to whole electroforming molten salt baths, the molar fraction sum of the molar fraction of LiBr and CsBr is at least 0.5 to less than among the embodiment 2～4 of 0.95 scope and the embodiment 6～9, is better than the molar fraction sum not at the embodiment 1 (0.45) of above-mentioned scope and the precipitation state of the Cr among the embodiment 5 (0.97) at the precipitation state of the Cr under 250 ℃ and 300 ℃.Find that embodiment 2～4 and embodiment 6～9 are more stable as the electroforming molten salt bath.
In addition, with respect to whole electroforming molten salt baths, the molar fraction sum of the molar fraction of LiBr and CsBr be at least 0.5 to less than the mol ratio of 0.95 scope and LiBr and CsBr at least 1.8 to the embodiment 2～4 of 2.5 scopes at the most with embodiment 7 and 8 in, when supplying 100mA/cm
2Electric current the time, the precipitation state of Cr is better than the not precipitation state of the Cr in the embodiment 6 (1.6) of above-mentioned scope and embodiment 9 (2.7) of mol ratio.Find embodiment 2～4 and embodiment 7 and 8 more stable as the electroforming molten salt bath.
And, (has LiBr: CsBr: KBr=56.1: among the embodiment 3 25: 18.9 mol ratio) having the eutectic component, not only at 300 ℃, and under 250 ℃ low temperature, the precipitation state of Cr is better than the precipitation state of the Cr among other embodiment with eutectic component greatly.Find that embodiment 3 is as electroforming molten salt bath quite stable at low temperatures.
To impose on the square Ni substrate surface that the length of side is 1cm by the photo-resist that PMMA forms with 50 μ m thickness.With this photo-resist of SR photoirradiation, and will be except that removing with the resist in the zone the zone of SR photoirradiation.On the Ni base material, formed like this have line/at interval (line/space) be the grid-like resist pattern of 50 μ m/50 μ m.
The Ni base material is immersed in the 500 gram electroforming molten salt baths 9 as electroformed mould 3, and described electroforming molten salt bath 9 is to be placed in the crucible that is shown in Fig. 2 electroforming apparatus 4.Here, electroforming molten salt bath 9 is by LiBr, and CsBr and KBr (mol ratio is LiBr: CsBr: KBr=56.1: 25: 18.9) form.With CrCl
2Add in the electroforming molten salt bath 9 with following amount: with respect to whole electroforming molten salt baths 9, its molar fraction reaches 0.01.
Then, be set in the temperature of electroforming molten salt bath 9 under 250 ℃ the state, to have current density in 50 minutes be 100mA/cm in supply between anode of being made up of Cr 7 and electroformed mould 3
2Electric current.After this, double the magnitude of current, and further supply the electric current 200 minutes of this doubled amount.So, on electroformed mould 3, obtained the electroforming product formed by Cr.Here, during electroforming,, progressively increase, and after 30 minutes, reach-0.80V from-0.90V at the electropotential of negative electrode with respect to reference electrode 13.After this, after the magnitude of current doubles, at once electropotential is dropped to-0.93V, and when the separation of electroforming, be increased to arrival-0.79V more subsequently.
After this, from electroforming apparatus 4, take out electroformed mould 3 and water flushing, remove the salt that is attached on the electroforming product of forming by Cr by this.Then, after dry electroformed mould 3 and electroforming product, the surface of polishing electroforming product is so that improve smoothness and adjust its thickness to 200 μ m.
At last, remove the resin that is attached on the electroforming product with plasma ashing, just obtained the metal products formed by Cr, wherein, described electroforming product mechanical separation from the electroformed mould 3, described metal products have the bossing that forms lattice-shaped and between projection with the bossing of grid-like arrangement.
The metal products of being made up of Cr of Huo Deing has 800 Vickers' hardness (HV) like this.Here, the metal products among the embodiment 10 also is under Ar atmosphere, prepares in the closed-loop operation case.
Comparative Examples 1
(have LiCl: KCl=45: the electroforming molten salt bath of 55 mass ratio) forming 9 is carried out the electroforming with the high temperature at 400 ℃, has obtained the metal products of being made up of Cr as mode same among the embodiment 10 by LiCl and KCl except using.Here, during electroforming,, progressively increase, and after 30 minutes, reach-0.76V from-0.85V at the electropotential of negative electrode with respect to reference electrode 13.Then, after the magnitude of current doubles, at once electropotential is dropped to-0.90V, and when the separation of electroforming, be increased to arrival-0.75V more subsequently.
During the metal products of being made up of Cr that obtains in SEM (scanning electronic microscope) observation Comparative Examples 1, the discovery resist pattern is not transferred on this metal products.This may be because because at 400 ℃ high temperature, the resist distortion during the electroforming on the electroformed mould 3 causes.
As mentioned above, according to the present invention, can provide a kind of permission at low temperatures electroforming the electroforming molten salt bath and use it to prepare the method for metal products.
Although describe and show the present invention in detail, should understand significantly, it only is in order to illustrate and example, is not in order to limit, design of the present invention and scope are only by the definition of term of appended claims.
Claims (7)
1. an electroforming molten salt bath (9), it comprises lithiumbromide, cesium bromide, and the halogenide of alkali-metal halogenide and/or alkaline-earth metal.
2. according to the electroforming molten salt bath (9) of claim 1, wherein
Described alkali-metal halogenide is Potassium Bromide.
3. according to the electroforming molten salt bath of claim 1, wherein
With respect to whole electroforming molten salt baths (9), the molar fraction sum of the molar fraction of described lithiumbromide and described cesium bromide is set at least 0.5 and arrives less than in 0.95 the scope.
4. according to the electroforming molten salt bath (9) of claim 1, wherein
Mol ratio lithiumbromide/the cesium bromide of described lithiumbromide and described cesium bromide is set at least 1.8 in 2.5 scope at the most.
5. according to the electroforming molten salt bath of claim 1, wherein
Described electroforming molten salt bath (9) has the eutectic component.
6. method for preparing metal products, it comprises the steps:
Go up a part that forms the resist pattern (2) and described conductive base (1) of exposing at conductive base (1);
The described conductive base (1) that has formed resist pattern (2) is immersed in the electroforming molten salt bath (9) according to claim 1, and this electroforming molten salt bath contains the compound of wanting sedimentary metal and/or wanting sedimentary metal; And
Exposed portion at conductive base (1) precipitates described metal.
7. according to the method for preparing metal products of claim 6, wherein
When the described metal of precipitation, the temperature of described electroforming molten salt bath (9) is set at 300 ℃ at the most.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003179788A JP3901133B2 (en) | 2003-06-24 | 2003-06-24 | Molten salt bath for electroforming and method for producing metal product using the same |
| JP179788/03 | 2003-06-24 | ||
| JP179788/2003 | 2003-06-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1572909A CN1572909A (en) | 2005-02-02 |
| CN100344796C true CN100344796C (en) | 2007-10-24 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2004100050435A Expired - Fee Related CN100344796C (en) | 2003-06-24 | 2004-02-16 | Molten salt bath for electroforming and method of manufacturing metal product using the same |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20040262163A1 (en) |
| JP (1) | JP3901133B2 (en) |
| KR (1) | KR101079892B1 (en) |
| CN (1) | CN100344796C (en) |
| DE (1) | DE102004014402A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845643A (en) * | 2009-03-27 | 2010-09-29 | 住友电气工业株式会社 | The method and the tungsten film of molten salt bath, the described molten salt bath of preparation |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4883534B2 (en) * | 2008-03-26 | 2012-02-22 | 住友電気工業株式会社 | Molten salt bath, method for producing molten salt bath, and tungsten precipitate |
| JP5544746B2 (en) * | 2009-04-20 | 2014-07-09 | 東ソー株式会社 | Method for producing metallic indium |
| CN102544536A (en) * | 2010-12-24 | 2012-07-04 | 中国电子科技集团公司第十八研究所 | Electrolyte for thermal battery and provided with 4-component inorganic fused salt |
| CN102569836A (en) * | 2010-12-24 | 2012-07-11 | 中国电子科技集团公司第十八研究所 | Preparation method of quadruple inorganic molten salt electrolyte |
| CN102437345A (en) * | 2011-12-19 | 2012-05-02 | 梅岭化工厂 | Thermal battery electrolyte with low melting point and high electric conductivity and preparation method thereof |
| US20140353159A1 (en) * | 2013-06-04 | 2014-12-04 | The Ohio State University | Electrochemical method of lithium iron arsenic superconductor preparation |
| US11136686B2 (en) * | 2015-07-16 | 2021-10-05 | Battelle Energy Alliance, Llc. | Methods and systems for aluminum electroplating |
| EP3546621A4 (en) * | 2016-11-22 | 2020-08-05 | Sumitomo Electric Industries, Ltd. | Titanium plating solution production method and titanium plated product production method |
| JP7097572B2 (en) * | 2018-08-31 | 2022-07-08 | 国立大学法人京都大学 | Manufacturing method of metallic titanium |
| US11746434B2 (en) | 2021-07-21 | 2023-09-05 | Battelle Energy Alliance, Llc | Methods of forming a metal coated article |
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| US6458218B1 (en) * | 2001-01-16 | 2002-10-01 | Linamar Corporation | Deposition and thermal diffusion of borides and carbides of refractory metals |
| JP2003213484A (en) * | 2002-01-16 | 2003-07-30 | Nippon Steel Corp | Mg-ADDED ELECTROGALVANIZING BATH, AND PLATING METHOD USING THE BATH |
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| US2935454A (en) * | 1953-05-01 | 1960-05-03 | Tokumoto Shin-Ichi | Method of the electrodeposition of titanium metal |
| US2913332A (en) * | 1957-04-05 | 1959-11-17 | Dow Chemical Co | Production of titanium metal |
| US3368949A (en) * | 1963-06-10 | 1968-02-13 | Bendix Corp | Process for electroforming inlaid circuits |
| US3371020A (en) * | 1964-12-14 | 1968-02-27 | Union Carbide Corp | Process for the electrodeposition of metals |
| US5215631A (en) * | 1982-06-25 | 1993-06-01 | Cel Systems Corporation | Electrolytic preparation of tin, other metals, alloys and compounds |
| US4564423A (en) * | 1984-11-28 | 1986-01-14 | General Dynamics Pomona Division | Permanent mandrel for making bumped tapes and methods of forming |
| US5647966A (en) * | 1994-10-04 | 1997-07-15 | Matsushita Electric Industrial Co., Ltd. | Method for producing a conductive pattern and method for producing a greensheet lamination body including the same |
| JP2004084059A (en) | 2002-07-04 | 2004-03-18 | Sumitomo Electric Ind Ltd | Die for plating with fine pattern, fine metal structure, die for fine working, method for producing die for plating with fine pattern, and method for producing fine metal structure |
-
2003
- 2003-06-24 JP JP2003179788A patent/JP3901133B2/en not_active Expired - Fee Related
-
2004
- 2004-02-12 US US10/776,264 patent/US20040262163A1/en not_active Abandoned
- 2004-02-16 CN CNB2004100050435A patent/CN100344796C/en not_active Expired - Fee Related
- 2004-03-24 DE DE102004014402A patent/DE102004014402A1/en not_active Withdrawn
- 2004-06-09 KR KR1020040042024A patent/KR101079892B1/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6458218B1 (en) * | 2001-01-16 | 2002-10-01 | Linamar Corporation | Deposition and thermal diffusion of borides and carbides of refractory metals |
| JP2003213484A (en) * | 2002-01-16 | 2003-07-30 | Nippon Steel Corp | Mg-ADDED ELECTROGALVANIZING BATH, AND PLATING METHOD USING THE BATH |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101845643A (en) * | 2009-03-27 | 2010-09-29 | 住友电气工业株式会社 | The method and the tungsten film of molten salt bath, the described molten salt bath of preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102004014402A1 (en) | 2005-01-13 |
| KR101079892B1 (en) | 2011-11-04 |
| US20040262163A1 (en) | 2004-12-30 |
| JP3901133B2 (en) | 2007-04-04 |
| JP2005015821A (en) | 2005-01-20 |
| KR20050001320A (en) | 2005-01-06 |
| CN1572909A (en) | 2005-02-02 |
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