CN1678768A - Method of treatment for reducing elution of lead from lead containing copper alloy and waterwork utensils made from lead containing copper alloy - Google Patents
Method of treatment for reducing elution of lead from lead containing copper alloy and waterwork utensils made from lead containing copper alloy Download PDFInfo
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- CN1678768A CN1678768A CN 03820699 CN03820699A CN1678768A CN 1678768 A CN1678768 A CN 1678768A CN 03820699 CN03820699 CN 03820699 CN 03820699 A CN03820699 A CN 03820699A CN 1678768 A CN1678768 A CN 1678768A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/07—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing phosphates
- C23C22/08—Orthophosphates
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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Abstract
A method of treatment for reducing the elution of lead from a lead-containing copper alloy, characterized in that it comprises immersing the lead-containing copper alloy in an acidic solution which is free of chromic acid and contains a phosphoric acid or its derivative, to remove the lead in a surface portion thereof; and waterwork utensils made of a lead-containing copper alloy and treated by the method. The utensils having been treated by the method exhibit satisfactorily effective reduction in the elution of lead, and also are free from significant discoloration and from the reduction of its commercial value due to discoloration since only a little etching takes place owing to an acidic phosphoric acid or its derivative and only a fine phosphate film is formed. Further, sodium chloride may be added, the lead-containing copper alloy may be, in advance, immersed in an alkaline etching fluid, to remove the lead in a surface portion thereof, and the outer surface of the alloy may have been plated with a metal such as nickel-chromium.
Description
Technical field
The present invention relates in order to reduce from the processing method of the plumbous stripping of the reduction of leaded copper alloy stripping lead and to have reduced the waterpipe utensil of the leaded copper alloy system of plumbous stripping.
The waterpipe utensil is tap accessory, waterpipe instrument, hot water machine member, warm water washing toilet seat member, boiler, water heater, water chiller, ice machine, water purifier, Lukewarm water boiler, automatic vending machine, ball formula tap, small containers, valve, spilling water valve, heat exchanger, joint, feedwater and hot water, pipe, draining table, commode, closet, bath, residential equipment parts etc., comprises the utensil that all is connected with feed pipe.
Background technology
Past, waterpipe is with utensil tap accessory for example, usually with the casting of the Cu alloy materials such as copper and bronze brass or forging, reorganize and outfit shape through machining, attrition process etc., implement the various surface treatments such as nickel plating chromium, application, ion plating, make via final goods assembling procedure. For above-mentioned copper alloy, in order to improve the processability such as machinability, mostly situation in the base material, adds plumbous, therefore should the ground stripping of lead trace in drinking water, when this water of long-term drinking, might give the human body bad influence, in recent years worry this problem.
The inventor is conceived to plumbous exist form and physical property thereof and has delivered such invention in No. the 3182765th, patent: by with leaded copper alloy impregnation process in alkaline corrosion liquid, chromic acid solution, chromate solution, reduce significantly the stripping of lead.
Among the method for the plumbous stripping of the reduction of record, delivered in No. the 3182765th, the patent: among the chromate processing method, contain at the same time the situation of the leaded copper alloy of dipping in the solution of chromic acid and phosphoric acid, with regard to reducing plumbous stripping, produce effect most. , flood the situation of leaded copper alloy in this chromate solution, the outward appearance of the copper alloy part behind the dipping is turned white, and becomes not bright-coloured variable color outward appearance, often lowers as commodity value. This is because by comprising the phosphorus chromate processing of chromic acid and phosphoric acid, formed the cause of coloured overlay film at copper alloy surface.
The present invention finishes for solving above-mentioned problem, the present invention seeks to, and provides not because of appearance color change to reduce the processing method of the plumbous stripping of reduction of leaded copper alloy of commodity value and the waterpipe utensil of leaded copper alloy system.
Summary of the invention
In order to achieve the above object, the 1st of the present invention is the processing method of the plumbous stripping of reduction of leaded copper alloy, it is characterized in that, leaded copper alloy is immersed in do not contain chromic acid in the solution but in the acid solution of phosphoric acid compound, remove the lead on surface.
So, because a little corrosive effect of acid phosphatase compound and only form the phosphoric acid overlay film of pettiness without large variable color, does not reduce commodity value yet. In addition, about reducing plumbous stripping sufficient effect is arranged also.
In order to achieve the above object, the 2nd of the present invention is the processing method of the plumbous stripping of reduction of leaded copper alloy, it is characterized in that, leaded copper alloy is immersed in do not contain chromic acid in the solution but in the acid solution of phosphoric acid compound and sodium chloride.
So, by an amount of sodium chloride that replenishes in the phosphate cpd of acidity, improve the carrying out of reaction, can guarantee corrosive effect, and increase phosphoric acid overlay film can be guaranteed stable outward appearance. Do not reduce commodity value yet. In addition, about reducing plumbous stripping sufficient effect is arranged also.
In order to achieve the above object, the 3rd of the present invention is the processing method of the plumbous stripping of reduction of leaded copper alloy, it is characterized in that, leaded copper alloy is immersed in the corrosive liquid of alkalescence, remove the lead on surface, then be immersed in and do not contain chromic acid in the solution but in the acid solution of phosphoric acid compound.
So, at first by being immersed in the alkaline corrosion liquid, can roughly optionally remove the lead of copper alloy surface, therefore namely in solution, do not contain chromic acid with subsequent handling but the effect of the plumbous stripping of reduction of the acid solution dipping process of phosphoric acid compound complements each other, can see more fully effect about reducing plumbous stripping yet. In addition, after these operations, because a little corrosive effect of acid phosphatase compound and only form the phosphoric acid overlay film of pettiness, so leaded copper alloy does not reduce commodity value without large variable color yet.
In order to achieve the above object, the 4th of the present invention is the processing method of the plumbous stripping of reduction of leaded copper alloy, it is characterized in that, leaded copper alloy is immersed in the corrosive liquid of alkalescence, remove the lead on surface, then be immersed in and in solution, do not contain chromic acid but in the acid solution of phosphoric acid compound and sodium chloride.
So, at first by being immersed in the alkaline corrosion liquid, can roughly optionally remove the lead of copper alloy surface, therefore namely in solution, do not contain chromic acid with subsequent handling but the effect of the plumbous stripping of reduction of the acid solution dipping process of phosphoric acid compound and sodium chloride complements each other, can see more fully effect about reducing plumbous stripping yet. In addition, after these operations, by an amount of sodium chloride that replenishes in the phosphate cpd of acidity, improve the carrying out of reaction, can guarantee corrosive effect, and the increase of phosphoric acid overlay film can be guaranteed stable outward appearance. Do not reduce commodity value yet. In addition, about reducing plumbous stripping sufficient effect is arranged also.
In order to achieve the above object, the 5th of the present invention is according to the processing method of the plumbous stripping of reduction of the described leaded copper alloy of invention the 1st and the 3rd, it is characterized in that main plating is processed outer surface, remove plating not mainly at the lead on inner surface.
So, the part that the plating of outer surface has been processed, at the dipping process of above-mentioned alkaline corrosion liquid with in solution, do not contain chromic acid but do not cause solubilizing reaction and corrosion reaction in the dipping process of the acid solution of phosphoric acid compound, therefore variable color not occuring, and can realize: thus only plating is not processed the effect that main inner surface that leaded copper alloy exposes reduces plumbous stripping. Certainly, interior surface thereof, because a little corrosive effect of acid phosphatase compound and only form the phosphoric acid overlay film of pettiness, so also can be with large variable color.
In order to achieve the above object, the 6th of the present invention is according to the processing method of the plumbous stripping of reduction of the 3rd described leaded copper alloy of invention, it is characterized in that, and mainly to the plating of outer surface, be the plating of implementing chromium plating after the nickel plating.
With the waterpipe utensil of the leaded copper alloy headed by the tap accessory,, corrosion resistance ornamental for outer surface is paid, wear resistance etc., the situation of implementing chromium plating after the nickel plating is many, is widely used plating always. In the situation of this plating, owing in the dipping process of the acid solution of the dipping process of above-mentioned alkaline corrosion liquid and phosphoric acid compound, do not cause solubilizing reaction and corrosion reaction, therefore variable color not occuring, and can realize: thus only plating is not processed the effect that main inner surface that leaded copper alloy exposes reduces plumbous stripping. Certainly, interior surface thereof, owing to only have a little corrosive effect of acid phosphatase compound and only form the phosphoric acid overlay film of pettiness, so also can be with large variable color.
In order to achieve the above object, the 7th of the present invention is the waterpipe utensil of the 1st the-the 6th described leaded copper alloy system of invention, it is characterized in that, is immersed in the acid solution that contains phosphate cpd.
So, because a little corrosive effect of acid phosphatase compound and only form the phosphoric acid overlay film of pettiness, therefore can about reducing plumbous stripping sufficient effect not arranged with the large variable color of leaded copper alloy surface yet, therefore can provide the waterpipe that does not reduce commodity value utensil.
The simple declaration of accompanying drawing
Fig. 1 is the figure that represents the bronze casting that uses in embodiments of the present invention tap accessory processed.
Before Fig. 2 (a) was the processing of the plumbous stripping of reduction of relevant leaded copper alloy of the present invention, the waterpipe of leaded copper alloy system (b) was its cross-section photograph with the surperficial enlarged photograph of utensil.
After Fig. 3 (a) was the processing of the plumbous stripping of reduction of relevant leaded copper alloy of the present invention, the waterpipe of leaded copper alloy system (b) was its cross-section photograph with the surperficial enlarged photograph of utensil.
The preferred forms of invention
By in solution, not containing chromic acid but flood in the acid solution of phosphoric acid compound of the present invention, because the phosphoric acid overlay film of a little corrosive effect of leaded copper alloy surface and formation pettiness, therefore not only in the plumbous stripping of reduction large reduction effect is arranged, and also do not have in appearance large variable color. This results from: the mixing overlay film with respect to chromium and phosphorus is coloured a little, and the independent overlay film of phosphoric acid is colourless.
By in solution, not containing chromic acid but an amount of activating agent sodium chloride that replenishes in the acid solution of phosphoric acid compound of the present invention, improve the carrying out of reaction, the formation of corrosive effect and small phosphoric acid overlay film increases, and can guarantee stable outward appearance.
Activating agent has sodium chloride, sodium sulphate, sodium fluoride, sodium nitrate etc., and addition is about 0.1-10g/L, often adds separately or adds several.
Phosphate cpd has potassium phosphate, sodium phosphate, calcium phosphate, ammonium phosphate, trbasic zinc phosphate etc., and addition is about 0.1-50g/L, often adds separately or adds several. In order to make the solution that has added these compounds be acid, add the inorganic acids such as phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid. Addition is about 0.1-50g/L, often adds separately or adds several. In addition, also can add the organic acids such as acetic acid, oxalic acid, citric acid, formic acid, butyric acid, propionic acid. The pH of solution below 2, is preferably below 1. As additive, the metallic compounds such as zinc, iron, copper, manganese, nickel also can suit to add. Phosphatic chemical surface treatment liquid also can be utilized them by extensively commercially available.
Treatment temperature is about normal temperature-70 ℃, the processing time be several seconds-between planting somewhat, determine according to shape and the suitable size of object being treated. The situation of the parts of complicated shape when flooding in solution, is noted avoiding producing bubble, in addition, in order to improve the efficient of processing, also can shake object being treated. After the processing, the bad order that causes in order to eliminate the residual and residual grade of moisture film of water droplet is wished fast washing, drying or the heated-air drying after the hot water wash of passing through of going forward side by side.
In solution, do not contain chromic acid but before in the acid solution of phosphoric acid compound impregnated in, also can be by being immersed in the alkaline corrosion liquid, optionally the lead of leaded copper alloy surface is removed in dissolving. Lead is amphoteric metal, does not form alloy and exist with plumbous simple substance form in copper alloy, and therefore by the effect of alkaline corrosion liquid, the copper alloy parent does not react substantially, can be only selectively dissolving remove lead compound. So, can alleviate and in solution, not contain chromic acid but burden in the dipping process of the acid solution of phosphoric acid compound. In addition, also working as removing the degreasing process that is attached to the dirts such as oil component on the leaded copper alloy in front operation, is very high efficiency operation therefore.
The principal component of alkaline corrosion liquid is one or more the alkaline solution that has dissolved among NaOH, potassium hydroxide, sodium carbonate, sodium phosphate, sodium phosphate trimer, sodium metasilicate, the sodium orthosilicate etc. Concentration is generally a few g/L-tens g/L, and is suitable normal by the combination of the composition that uses. Treatment temperature is about 60-90 ℃, and the processing time is between a few minutes-dozens of minutes, determines according to shape and the suitable size of object being treated. The situation of the parts of complicated shape when flooding in solution, is noted avoiding producing bubble, in addition, in order to improve treatment effeciency, also can shake object being treated. After the processing, preferred fast washing enters into next operation.
In order to improve the soaking into of alkaline corrosion liquid, wetability, for the purpose that reduces surface tension of liquid, also can add surfactant. As surfactant, mostly use anion surfactant or non-ionic surface active agent, use separately or also use these materials. As anion surfactant, higher fatty acids sodium, sulfated oil, higher alcohol sulfate sodium, alkylbenzene sodium sulphate, senior alkyl ether sodium sulfovinate, alpha-olefin sodium sulphate are arranged. In addition, as non-ionic surface active agent, alkyl polyoxyethylene ether, alkyl phenyl APEO, aliphatic acid ethylene oxide adduct, polypropylene glycol ethylene oxide adduct (Pu Luluonike) are arranged. Addition is generally a few g/L-tens g/L.
In addition, adhere to again in order to prevent lead from becoming hydroxide, promote simultaneously plumbous dissolving, can in alkaline corrosion liquid, add chelating agent. As chelating agent, easily form the compound of complex with lead such as preferred EDTA, ethylenediamine, triethanolamine, thiocarbamide, Rochelle salt, tartaric acid etc. Addition is generally a few g/L-tens g/L.
When in alkaline corrosion liquid, adding oxidant, plumbous oxidized, occur via lead oxide (PbO2) be dissolved in again the step reaction of 2 in the alkali. This reaction is because to be dissolved in 1 step reaction of alkali than lead fast, so the result promotes plumbous the removal, can improve to remove efficient, shorten the processing time. As the inorganic compounds such as organic oxidation compound, hypochlorite, bleaching powder, hydrogen peroxide, potassium permanganate, persulfate, perchlorate such as use m-nitrobenzene sodium sulfonate, sodium paranitrobenzoate of oxidant. Addition is generally a few g/L-tens g/L.
With the waterpipe utensil headed by the tap accessory, for purposes such as specious, corrosion resistance, wear resistances, sometimes implement plating, its manufacture method, after usually carrying out known plating preliminary treatment, carry out plating, chemical plating, displacement plating or dry type plating as known technology, therefore be not particularly limited. In these method for plating, the situation of chromium plating is the most general from quality, cost aspect after the employing galvanoplastic enforcement nickel plating. Gold-plated, silver-plated, rhodanizing, platinum plating, copper facing, zinc-plated, zinc-plated cobalt alloy, zinc-plated nickel alloy etc. are arranged beyond that. As the dry type method for plating, vacuum evaporation, ion plating, sputter, CVD method etc. are arranged, titanium nitride, titanium carbide, zirconium nitride, chromium nitride, carborundum, diamond, aluminium oxide, titanium carbonitride etc. are arranged.
These platings mostly substantially be not with plating layer with the leaded copper alloy water making pipe road headed by the tap accessory with the surface, inside of utensil in the situation, so this part are the state that copper alloy matrix exposes. The present invention is by will this leaded copper alloy being immersed in above-mentioned alkaline corrosion liquid or not containing chromic acid but in the acid solution of phosphoric acid compound in solution, do not cause any variation with the part of plating layer, and effectively removes the lead of copper alloy exposed portions serve.
(embodiment)
Be described more specifically by the following examples the present invention, but the present invention is not limited thereto, in technological thought scope of the present invention, certainly can carries out a lot of changes.
Under condition shown below, use the bronze casting tap accessory processed of Fig. 1 record, under various treatment conditions, carry out plumbous Transformatin, estimate the effect (experiment 1) of apparent condition and the plumbous stripping of reduction.
The order that treatment process is processed in acid solution after processing by caustic corrosion is carried out. Fig. 2 (a), (b) and Fig. 3 (a), (b) be before and after treatment surperficial enlarged photograph and the enlarged photograph in cross section. Relatively these photos are known, and are after processing, plumbous from the part stripping of surperficial 5-6 μ m.
Outward appearance is through visual valuation, and the effect that reduces plumbous stripping has been analyzed the lead concentration of stripping according to JIS-S-3200-7 (2000) " waterpipe with utensil-leaching performance test method ". Table 1 has gathered state and the lead release for the treatment of conditions, outward appearance. The condition of caustic corrosion is to use the liquid of NaOH 50g/L+ sodium paranitrobenzoate 1g/L, unifies the condition with 80 ℃, 10 minutes.
The state of outward appearance, variable color seriously is judged to be in the rank of the very large problem of commodity existence *, will there be variable color in-problem rank on commodity to be judged to be △, will substantially there be variable color no problem rank on commodity to be judged to be zero.
Treatment conditions and the experimental result of table 1 experiment 1
| The treatment conditions in acid solution of carrying out after the caustic corrosion | The state of outward appearance | Lead release (ppb) | |||
| Chromic anhybride concentration (g/L) | 85% phosphoric acid concentration (ml/L) | Treatment temperature (℃) | Processing time (second) | ||
| 10 | 10 | 50 | 30 | △ | 3 |
| 50 | Do not add | 50 | 30 | ○ | 15 |
| Do not add | 10 | 50 | 30 | ○ | 10 |
| 10 | 10 | 50 | 300 | × | 1 |
| 50 | Do not add | 50 | 300 | ○ | 5 |
| Do not add | 10 | 50 | 300 | ○ | 3 |
| Only carry out caustic corrosion, in acid solution, do not process. | ○ | 39 | |||
| Product are untreated. | ○ | 880 | |||
Clearly known by these results, the processing in the acid solution that contains chromic anhybride and phosphoric acid, appearance color change, but the processing in single separately acid solution, outward appearance is also no problem, and lead release was few when mono phosphoric acid ester was stayed alone reason.
Secondly, carry out plumbous processing of removal under the state that has added sodium chloride, estimated the state of outward appearance and the effect (experiment 2) of the plumbous stripping of reduction. The order that treatment process is processed in acid solution after processing by caustic corrosion is carried out. Ocular estimate method and the effect that reduces plumbous stripping have been analyzed the lead concentration of stripping according to JIS-S-3200-7 (2000) " waterpipe with utensil-leaching performance test method ". Table 2 has gathered state and the lead release for the treatment of conditions, outward appearance. The condition of caustic corrosion is to use the liquid of NaOH 50g/L+ sodium paranitrobenzoate 1g/L, unifies the condition with 60 ℃, 5 minutes.
The state of outward appearance, variable color seriously is judged to be in the rank of the very large problem of commodity existence *, to there be variable color in-problem rank on commodity to be judged to be △, with substantially there not being variable color no problem rank on commodity to be judged to be zero, nondiscolouring no problem rank on commodity is judged to be ◎.
Treatment conditions and the experimental result of table 2 experiment 2
| The processing in acid solution of carrying out after the caustic corrosion | The state of outward appearance | Lead release (ppb) | |||
| 85% phosphoric acid concentration (ml/L) | Sodium chloride (g/L) | Treatment temperature (℃) | Processing time (second) | ||
| 10 | - | 55 | 300 | ○ | 2 |
| 10 | 0.5 | 55 | 300 | ◎ | 2 |
Clearly known by these results, the processing in the acid solution that contains sodium chloride and phosphoric acid, appearance color change is further suppressed, and lead release is also no problem.
Secondly, about bronze casting tap accessory processed of Fig. 1 of having implemented chromium plating after the nickel plating, under various treatment conditions, remove plumbous the processing, judged the state of outward appearance and reduced the effect (testing 3) of plumbous stripping. The order that treatment process is processed in acid solution after processing by caustic corrosion is carried out. The evaluation method of ocular estimate method and lead release also adopts and tests 1 identical method and carry out, outward appearance is through visual valuation, and the effect that reduces plumbous stripping has been analyzed the lead concentration of stripping according to JIS-S-3200-7 (2000) " waterpipe with utensil-leaching performance test method ". Table 3 has gathered state and the lead release for the treatment of conditions, outward appearance. The condition of caustic corrosion is to use the liquid of NaOH 50g/L+ sodium paranitrobenzoate 1g/L, unifies the condition with 60 ℃, 5 minutes.
The state of outward appearance, variable color seriously is judged to be in the rank of the very large problem of commodity existence *, will there be variable color in-problem rank on commodity to be judged to be △, will substantially there be variable color no problem rank on commodity to be judged to be zero,
Treatment conditions and the experimental result of table 3 experiment 3
| The processing in acid solution of carrying out after the caustic corrosion | The state of outward appearance (inner bronze part) ※ 1 | Lead release (ppb) | |||
| Chromic anhybride concentration (g/L) | 85% phosphoric acid concentration (ml/L) | Treatment temperature (℃) | Processing time (second) | ||
| 10 | 10 | 50 | 30 | △ | 2 |
| 50 | Do not add | 50 | 30 | ○ | 10 |
| Do not add | 10 | 50 | 30 | ○ | 9 |
| 10 | 10 | 50 | 300 | × | 1 |
| 50 | Do not add | 50 | 300 | ○ | 4 |
| Do not add | 10 | 50 | 300 | ○ | 2 |
| Only carrying out caustic corrosion does not process in acid solution. | ○ | 12 | |||
| Product are untreated. (nickel plating chromium product) | ○ | 18 | |||
※ 1: it is unusual that the nickel plating chromium on surface partly has no variable color etc.
Clearly known by these results, even nickel plating chromium product, in the processing in the acid solution that contains chromic anhybride and phosphoric acid, though the bronze section variable color on inner surface, but the processing in single separately acid solution, outward appearance are also no problem, and lead release was few when mono phosphoric acid ester was stayed alone reason. In addition, the nickel plating chromium part on surface can not see that fully variable color etc. is unusual, also can confirm to utilize the method for the plumbous stripping of reduction of the present invention about the plating product.
The effect of the present invention below above-mentioned formation performance. That is, because a little corrosive effect of acid phosphatase compound and only form the phosphoric acid overlay film of pettiness, so can be with large variable color, commodity value does not reduce yet. In addition, by in solution, not containing chromic acid but an amount of activating agent sodium chloride that replenishes in the acid solution of phosphoric acid compound of the present invention, improve the carrying out of reaction, the formation of corrosive effect and small phosphoric acid overlay film increases, can guarantee stable outward appearance, about reducing plumbous stripping sufficient effect be arranged also. In addition, at first by being immersed in the alkaline corrosion liquid, can roughly optionally remove the lead of copper alloy surface, therefore namely in solution, do not contain chromic acid with subsequent handling but the effect of the plumbous stripping of reduction of the acid solution dipping process of phosphoric acid compound complements each other, can see more fully effect about reducing plumbous stripping yet. In addition, after these operations, leaded copper alloy can be with large variable color, and commodity value does not reduce yet.
The part that the plating of outer surface has been processed, at the dipping process of above-mentioned alkaline corrosion liquid with in solution, do not contain chromic acid but do not cause solubilizing reaction and corrosion reaction in the dipping process of the acid solution of phosphoric acid compound, therefore variable color not occuring, and can realize: thus only plating is not processed the effect that main inner surface that leaded copper alloy exposes reduces plumbous stripping. Certainly, interior surface thereof can be with large variable color yet.
With the waterpipe utensil of the leaded copper alloy headed by the tap accessory,, corrosion resistance ornamental for outer surface is paid, wear resistance etc., the situation of implementing chromium plating behind the nickel plating chromium is many, is widely used plating always. In the situation of this plating, because at the dipping process of above-mentioned alkaline corrosion liquid with in solution, do not contain chromic acid but do not cause solubilizing reaction and corrosion reaction in the dipping process of the acid solution of phosphoric acid compound, therefore variable color not occuring, and can realize: thus only plating is not processed the effect that main inner surface that leaded copper alloy exposes reduces plumbous stripping. Certainly, interior surface thereof can be with large variable color yet.
In the present embodiment, before the dipping process of the acid solution of phosphoric acid compound, carried out the plating processing, processed but also can behind dipping process, carry out plating.
Industrial applicability
About the processing method of the plumbous stripping of reduction of leaded copper alloy of the present invention and leaded copper alloy water making pipe logos and utensils prodigiosin are enough in the various utensils that link to each other with feed pipe.
Claims (7)
1. the processing method of the plumbous stripping of the reduction of a leaded copper alloy is characterized in that, leaded copper alloy is immersed in do not contain chromic acid in the solution but in the acid solution of phosphoric acid compound.
2. the processing method of the plumbous stripping of the reduction of a leaded copper alloy is characterized in that, leaded copper alloy is immersed in do not contain chromic acid in the solution but in the acid solution of phosphoric acid compound and sodium chloride.
3. the processing method of the plumbous stripping of the reduction of a leaded copper alloy is characterized in that, leaded copper alloy is immersed in the lead of removing the surface in the corrosive liquid of alkalescence, then is immersed in not contain chromic acid in the solution but in the acid solution of phosphoric acid compound.
4. the processing method of the plumbous stripping of the reduction of a leaded copper alloy, it is characterized in that, leaded copper alloy is immersed in the lead of removing the surface in the corrosive liquid of alkalescence, then is immersed in and does not contain chromic acid in the solution but in the acid solution of phosphoric acid compound and sodium chloride.
5. according to the processing method of the plumbous stripping of reduction of the described leaded copper alloy of 1 of claim the and the 3rd, it is characterized in that, mainly is that outer surface carries out plating and processes.
6. according to the processing method of the plumbous stripping of reduction of the described leaded copper alloy of 5 of claims the, it is characterized in that, mainly to the plating of outer surface, is the plating of implementing chromium plating after the nickel plating.
7. the waterpipe utensil of the described leaded copper alloy system of 1 the-the 6th of claim the is characterized in that, is immersed in not contain chromic acid in the solution but contain in the acid solution of phosphate cpd.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002256207 | 2002-08-30 | ||
| JP256207/2002 | 2002-08-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1678768A true CN1678768A (en) | 2005-10-05 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03820699 Pending CN1678768A (en) | 2002-08-30 | 2003-08-29 | Method of treatment for reducing elution of lead from lead containing copper alloy and waterwork utensils made from lead containing copper alloy |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPWO2004024987A1 (en) |
| CN (1) | CN1678768A (en) |
| AU (1) | AU2003257600A1 (en) |
| WO (1) | WO2004024987A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143890A (en) * | 2013-03-04 | 2013-06-12 | 阮伟光 | Manufacturing method for low lead copper alloy bath utensil |
| CN106086894A (en) * | 2016-06-23 | 2016-11-09 | 台州德尊洁具厂(普通合伙) | A kind of tap main body deleading technique, tap main body remove lead equipment and the processing technique of tap main body |
| CN108348047A (en) * | 2015-11-11 | 2018-07-31 | Ykk株式会社 | Slide fastener coupling element band and its manufacturing method and slide fastener |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4197269B2 (en) * | 2002-09-09 | 2008-12-17 | 株式会社キッツ | Nickel elution prevention method for copper alloy piping equipment such as valves and fittings and its copper alloy piping equipment |
| CN1930324B (en) * | 2004-03-05 | 2012-02-08 | 株式会社开滋 | Method of preventing nickel leaching from copper alloy made liquid-contact equipment item, protective film forming agent for nickel leaching prevention and cleaner for nickel leaching prevention |
| JP4463278B2 (en) * | 2004-09-28 | 2010-05-19 | 株式会社早川バルブ製作所 | Hexavalent chromium-free surface treatment method and hexavalent chromium-free lead-containing copper-based metal material |
| JP5473781B2 (en) * | 2009-06-01 | 2014-04-16 | 株式会社Ｌｉｘｉｌ | Manufacturing method and processing method for lead-containing copper alloy water supply equipment |
| KR101782697B1 (en) * | 2015-12-11 | 2017-09-28 | 엄영호 | Water meter and method for manufacturing |
| ES2914290T3 (en) | 2016-07-05 | 2022-06-08 | Ngk Spark Plug Co | ceramic heater |
| JP6679511B2 (en) * | 2016-07-05 | 2020-04-15 | 日本特殊陶業株式会社 | Ceramic heater |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6324074A (en) * | 1986-07-17 | 1988-02-01 | Nippon Denso Co Ltd | Chemical conversion treatment bath composition for copper alloy |
| CN1207442C (en) * | 1997-12-03 | 2005-06-22 | 东陶机器株式会社 | Method of reducing elution of lead in lead-containing copper alloy, and ware made of lead-contg copper alloy |
-
2003
- 2003-08-29 CN CN 03820699 patent/CN1678768A/en active Pending
- 2003-08-29 WO PCT/JP2003/011093 patent/WO2004024987A1/en active Application Filing
- 2003-08-29 AU AU2003257600A patent/AU2003257600A1/en not_active Abandoned
- 2003-08-29 JP JP2004535893A patent/JPWO2004024987A1/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143890A (en) * | 2013-03-04 | 2013-06-12 | 阮伟光 | Manufacturing method for low lead copper alloy bath utensil |
| CN108348047A (en) * | 2015-11-11 | 2018-07-31 | Ykk株式会社 | Slide fastener coupling element band and its manufacturing method and slide fastener |
| CN108348047B (en) * | 2015-11-11 | 2020-10-02 | Ykk株式会社 | Fastener stringer, method for manufacturing same, and slide fastener |
| CN106086894A (en) * | 2016-06-23 | 2016-11-09 | 台州德尊洁具厂(普通合伙) | A kind of tap main body deleading technique, tap main body remove lead equipment and the processing technique of tap main body |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2004024987A1 (en) | 2004-03-25 |
| JPWO2004024987A1 (en) | 2006-01-12 |
| AU2003257600A1 (en) | 2004-04-30 |
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