CN1300382C - Steel components and parts covered by Zn-Fe-RE cladding material, electroplating method and electrolyte - Google Patents
Steel components and parts covered by Zn-Fe-RE cladding material, electroplating method and electrolyte Download PDFInfo
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- CN1300382C CN1300382C CNB2004100223082A CN200410022308A CN1300382C CN 1300382 C CN1300382 C CN 1300382C CN B2004100223082 A CNB2004100223082 A CN B2004100223082A CN 200410022308 A CN200410022308 A CN 200410022308A CN 1300382 C CN1300382 C CN 1300382C
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Abstract
The present invention relates to a steel component and part, an electroplating method and an electrolytic solution, wherein the surface of the steel component and part is plated with a Zn-Fe-RE composite plating layer. The present invention belongs to the technical field of the surface treatment of the steel component and part and a metal material. The corrosion-resistant Zn-Fe-RE composite plating layer is plated on the surface of the component and part, the electroplating method is adopted, and plating liquids are the electrolytic solution which uses chlorine salts of Fe and Zn as main salts and contains rare earth. The Zn-Fe-RE composite plating layer can be obtained by controlling the content of Fe salts, Zn salts and rare earth, the PH value of the plating liquids and the current density. The present invention has the advantages of simple technical method and plating liquid, no need for passivation, little environment pollution, high productive safety, low integrated cost, high corrosion resisting properties of the plating layer, favorable compactness, ornamental properties (appearance) and integrated properties, etc.
Description
Technical field: the present invention relates to steel-iron components and electro-plating method and electrolytic solution that a kind of coating surface has the Zn-Fe-RE composite deposite, belong to iron and steel parts and metal material surface processing technology field.
Technical background: corrosion and corrosion protection is related to Economic development and people's life safety, and surface engineering technology is to solve component of machine and material corrosion and most economical effective means of protection and method.Along with the develop rapidly of modern industry and science and technology, more and more higher to the performance requriements of component of machine and material surface, process for treating surface has also had development rapidly thereupon.Surface engineering technology can use chemistry, physics or electrochemical method to come component or material surface are handled, and makes its surface form various protective layers, improves the work-ing life of component or material.Alloy compound surface deposition (galvanic deposit or electroless plating) compare with the monometallic surface deposition because of it have higher solidity to corrosion, hardness, compactness, wear resistance, high thermal resistance, weldability and beautiful outward appearance, and obtained using widely.
Zinc-plated protective coating as iron and steel, the aboundresources low price because of zinc has obtained widespread use.In order to satisfy to component or material property requirements at the higher level, all strengthened research and application to the plating of zinc base alloys such as Zn-Ni, Zn-Fe, Sn-Zn, Zn-Co, Zn-Mn, Zn-Cr, Zn-Ti, Zn-Co-Cr, Zn-Co-Fe, Zn-Ni-P, Zn-Fe-P both at home and abroad, what wherein application was wider mainly is the alloy (Zn-Fe, Zn-Ni, Zn-Co) that zinc and iron family metal form.Studies show that the protective of zinc base alloy coating, ornamental, hardness and other mechanical property all are better than traditional zinc coating, are with a wide range of applications; Particularly zinc-iron alloy is because of having cost performance preferably, in German automobiles industry widespread usage.
Closely during the last ten years, people plate research and development high anti-corrosion zinc base alloy and have given very big concern.On the basis of constantly improving the compound plating of galvanic deposit zinc-base, developed Zn-TiO
2, Zn-Al
2O
3, Zn-SiO
2, etc. the composite deposite product and the technology of better performances, have better solidity to corrosion and other performances in order to make composite deposite, developed Zn-Fe-TiO in recent years again
2, Zn-Co-TiO
2, Zn-Ni-TiO
2Deng titanium is zinc bace composite coating layer.
However, both at home and abroad to the research of rare earth and zinc base alloy galvanic deposit and application also seldom, especially research and the application to Zn-Fe-RE yet there are no report.Though existing Zn-Fe, Zn-Ni Quito unit electroless plating coating have certain compactness and ornamental (outward appearance), its solidity to corrosion is still good inadequately, does not satisfy the needs of some a particular job environment; And Zn-SiO
2Hardness, wear resistance, high thermal resistance etc. nonmetal diffusing particle composite deposite are better, but its solidity to corrosion, compactness, ornamental (outward appearance) are relatively poor again.And most of zinc base alloys (comprise zn-fe alloy, Zn-Fe-TiO
2Deng) coating contains Fe amount lower (Fe%＜1%); therefore must could guarantee the high anti-corrosion of coating through the high chromic acid content Passivation Treatment; have very highly toxic chromic acid in the passivation technology, brought a lot of difficulties, safety in production and environmental protection cost are improved greatly to electroplating technology and plating bath aftertreatment.Zn and Co, TiO
2, elements such as Ni, Co plating rare because of the resource of these alloying elements also, use cost is higher.
Summary of the invention: the objective of the invention is to overcome the deficiencies in the prior art, provide a kind of and have that high anti-corrosion, high compactness, ornamental (outward appearance) are good, the iron and steel parts of the Zn-Fe-RE of high comprehensive performance base composite table surface layer, and do not need that Passivation Treatment, simple, safety, comprehensive cost are low, the iron and steel parts Zn-Fe-RE method for electroplating surface and the electrolytic solution of environmental protection.
Technology contents of the present invention is: coating surface has the iron and steel parts of Zn-Fe-RE coating, and described coating is the Zn-Fe-RE composite deposite that contains zinc, iron and rare earth element.The thickness of coating is 10
-2To 20 * 10
-3Mm, its special character are that the content range of various metallic elements in the coating is zinc 78% to 88%, iron 8% to 12%, rare earth element 0.5% to 10% by weight.Rare earth element can be any or several arbitrary combination in all rare earth elements (that is: cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, yttrium).Thickness of coating and each constituent content are determined in given range according to actual needs.
Iron and steel parts surface Zn-Fe-RE composite electric plating method, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into the plating tank electroplate liquid again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from plating bath; Described electroplate liquid includes as the villaumite of the Fe of main salt and Zn, as the citric acid of Synergist S-421 95, as (the NH of conducting salt
4)
2SO
4, as the H of buffer reagent
3BO
3, and rare-earth salts or rare earth oxide, its special character is that it consists of: FeCl
2100～200g/L, ZnCl
250～100g/L, (NH
4)
2SO
470～140g/L, citric acid 20～70g/L, H
3BO
320～40g/L, xitix 0.8～1.5g/L, rare-earth salts or rare earth oxide 1～20g/L, additive 0.5～5g/L.Additive is a polyoxyethylene glycol, thiocarbamide, Vanillin, in the tonka bean camphor any or several arbitrary combination, rare-earth salts or rare earth oxide are rare-earth chlorination salt, rare earth sulfate, in the rare earth oxide any or several arbitrary combination (that is: cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, the oxide compound of yttrium, the arbitrary combination of any one or more in villaumite or the vitriol, as: Lanthanum trichloride, Cerium II Chloride, Yttrium trichloride, cerous sulfate, lanthanum sulfat, praseodymium sulfate, cerium oxide, Praseodymium trioxide, europium sesquioxide, Scium trioxide etc.), the pH value of plating bath is 3～5, and the current density of plating is 1～8A/dm
2, temperature is room temperature.
The content of each constituent, processing parameter such as choose and plating time can specifically be selected according to the required thickness of coating of reality, hardness, density etc. in providing scope.
This plating electrolytic solution be include villaumite as the Fe of main salt and Zn, as the citric acid of Synergist S-421 95, as (the NH of conducting salt
4)
2SO
4, as the H of buffer reagent
3BO
3, and rare-earth salts or rare earth oxide, its special character is specifically to consist of: FeCl
2100～200g/L, ZnCl
250～100g/L, (NH
4)
2SO
470～140g/L, citric acid 20～70g/L, H
3BO
320～40g/L, xitix 0.8～1.5g/L, rare-earth salts or rare earth oxide 1～20g/L, additive 0.5～5g/L.Rare-earth salts or rare earth oxide are rare-earth chlorination salt, rare earth sulfate, in the rare earth oxide any or several arbitrary combination (that is: cerium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, the oxide compound of yttrium, the arbitrary combination of any one or more in villaumite or the vitriol, as: Lanthanum trichloride, Cerium II Chloride, Yttrium trichloride, cerous sulfate, lanthanum sulfat, praseodymium sulfate, cerium oxide, Praseodymium trioxide, europium sesquioxide, Scium trioxides etc.), additive is a polyoxyethylene glycol, thiocarbamide, Vanillin, in the tonka bean camphor any or several arbitrary combination.
The content of each constituent, processing parameter such as choose and in providing scope, specifically to select according to actual needs.
The present invention adopts Zn-Fe-RE electroplate liquid and electro-plating method, obtains the iron and steel parts that coating surface has Zn-Fe-RE coating, and making in Zn, the Fe hypothallus has increased rare earth alloy.Because the special electron structure of rare earth element makes it have outstanding chemically reactive; The adding of rare earth element can increase cathodic polarization, the galvanic deposit of resistance alloy when electroplating on the one hand, thereby make grain refining, and it is smooth careful that coating becomes, and solidity to corrosion improves; Direct and the Zn-Fe formation coating matrix of rare earth alloy element can form metallic compound, thereby the solidity to corrosion of coating is significantly improved in matrix on the other hand.And owing to Fe in the plating bath
2+Quantity big, make in the coating Fe content bigger, make coating outward appearance light, the good compactness that has and the advantage of ornamental (outward appearance).In acidic medium, the reaction of coating and medium mainly is zinc, iron and H
+Reaction, the solidity to corrosion of coating depends primarily on matrix metal and H
+The speed degree of reaction, and the specific activity zinc of iron in acid is poor, so higher Fe content improves its solidity to corrosion to acid in the coating.In addition, zinc base alloy is made anodic coating, can sacrifice the zinc in the coating, thus the protection matrix.Owing to the Fe content higher in the coating and the effect of rare earth alloy element, make coating not need Passivation Treatment just can reach higher solidity to corrosion, simplified the production technique link greatly, reduced environmental pollution, improved production security.Simultaneously, the aboundresources of rare earth, with low cost.Therefore, the present invention has processing method and plating bath efficient height, advantages such as energy consumption is low, flow process is short, environmental protection, low cost, and the iron and steel parts that is coated with this coating has high anti-corrosion, high compactness and ornamental.
Description of drawings: accompanying drawing is a process flow sheet of the present invention.
Embodiment: essence of the present invention is described further below in conjunction with drawings and Examples.
Embodiment 1: coating surface has the steel pipe of Zn-Fe-cerium coating, and coating is the Zn-Fe-cerium composite deposite that contains zinc, iron and Ce elements.The thickness of coating is 10
-2Mm, the content range of various metallic elements is zinc 88% by weight in the coating, iron 11.5%, cerium 0.5%.
Before this steel tube surface Zn-Fe-cerium composite plating method is included in and electroplates to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electrolytic solution again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from electrolytic solution.The pH value of electrolytic solution is 5, and galvanized current density is 3A/dm
2, temperature is room temperature, electroplating time is 0.5 hour.
This electrolytic solution be include villaumite as the Fe of main salt and Zn, as the citric acid of Synergist S-421 95, as (the NH of conducting salt
4)
2SO
4, as the H of buffer reagent
3BO
3, and the electroplate liquid of cerium salt, it specifically consists of: FeCl
2190g/L, ZnCl
2100g/L, (NH
4)
2SO
41300g/L, citric acid 30g/L, H
3BO
320g/L, xitix 0.8g/L, Cerium II Chloride 1g/L, polyoxyethylene glycol additive 0.5g/L.
This corrosion of coating parameter testing result is (comparing with iron-based body, zinc-plated, zinc-plated-iron):
| Plating | i(A/cm 2) | -Ecorr(V) |
| The iron-based body | 64 | 0.46 |
| Zinc-plated | 56 | 0.98 |
| Zinc-plated-iron | 32 | 1.02 |
| Zinc-plated-iron-rare earth | 22 | 1.0 |
Embodiment 2: coating surface has the guardrail of Zn-Fe-RE coating, and coating is the Zn-Fe-lanthanum composite deposite that contains zinc, iron and lanthanum element.The thickness of coating is 20 * 10
-3Mm, the content range of various metallic elements is zinc 78% by weight in the coating, iron 12%, lanthanum 10%.
The Zn-Fe-lanthanum method for electroplating surface of this guardrail, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electrolytic solution again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from electrolytic solution.The pH value of electrolytic solution is 3, and galvanized current density is 8A/dm
2, temperature is room temperature, electroplating time is 2.5 hours.
This electrolytic solution be include villaumite as the Fe of main salt and Zn, as the citric acid of Synergist S-421 95, as (the NH of conducting salt
4)
2SO
4, as the H of buffer reagent
3BO
3, and the electroplate liquid of lanthanum salt, it specifically consists of: FeCl
2200g/L, ZnCl
250g/L, (NH
4)
2SO
4140g/L, citric acid 20g/L, H
3BO
340g/L, xitix 1.5g/L, lanthanum sulfat 20g/L, thiourea additives 5g/L.
Embodiment 3: coating surface has the rolling screen door of Zn-Fe-yttrium coating, and coating is the Zn-Fe-yttrium-gadolinium-terbium-dysprosium-holmium-erbium-thulium-ytterbium-lutetium composite deposite that contains zinc, iron and yttrium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium rare earth element.The thickness of coating is 13 * 10
-3Mm, the content range of various metallic elements is zinc 84% by weight in the coating, iron 8%, yttrium 1%, gadolinium 1%, terbium 1%, dysprosium 1%, holmium 0.5%, erbium 0.5%, thulium 1%, ytterbium 1%, lutetium 1%.
Zn-Fe-yttrium-gadolinium-terbium-dysprosium-holmium-erbium-thulium-the ytterbium of this rolling screen door-lutetium method for electroplating surface, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electrolytic solution again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from electrolytic solution.The pH value of electrolytic solution is 4, and galvanized current density is 1A/dm
2, temperature is room temperature, electroplating time is 1.5 hours.
This electrolytic solution be include villaumite as the Fe of main salt and Zn, as the citric acid of Synergist S-421 95, as (the NH of conducting salt
4)
2SO
4, as the H of buffer reagent
3BO
3, and the electroplate liquid of yttrium oxide, gadolinium sesquioxide, sulfuric acid terbium, Dysprosium trichloride, Holmium trichloride, Erbium trioxide, thulium sulfate, ytterbium sulfate, lutecium chloride, it specifically consists of: FeCl
250g/L, ZnCl
260g/L, (NH
4)
2SO
470g/L, citric acid 70g/L, H
3BO
330g/L, xitix 1g/L, yttrium oxide 2g/L, gadolinium sesquioxide 2g/L, sulfuric acid terbium 2g/L, Dysprosium trichloride 2g/L, Holmium trichloride 1g/L, Erbium trioxide 1g/L, thulium sulfate 2g/L, ytterbium sulfate 2g/L, lutecium chloride 2g/L, polyoxyethylene glycol 2g/L, thiocarbamide 1g/L.
Embodiment 4: coating surface has the decorative steel plate of Zn-Fe-cerium-lanthanum coating, and coating is the Zn-Fe-cerium-lanthanum composite deposite that contains zinc, iron and cerium, lanthanum element.The thickness of coating is 14 * 10
-3Mm, the content range of various metallic elements is zinc 86% by weight in the coating, iron 10%, lanthanum 2%, cerium 2%.
Zn-Fe-cerium-lanthanum the method for electroplating surface of this steel plate, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electrolytic solution again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from electrolytic solution.The pH value of electrolytic solution is 4, and galvanized current density is 6A/dm
2, temperature is room temperature, electroplating time is 1.5 hours.
This electrolytic solution be include chloride salt as the Fe of main salt and Zn, as the citric acid of Synergist S-421 95, as (the NH of conducting salt
4)
2SO
4, as the H of buffer reagent
3BO
3, and the electroplate liquid of Cerium II Chloride, Lanthanum trichloride, it specifically consists of: FeCl
2170g/L, ZnCl
290g/L, (NH
4)
2SO
4110g/L, citric acid 35g/L, H
3BO
335g/L, xitix 1.2g/L, Cerium II Chloride 4g/L, Lanthanum trichloride 4g/L, polyoxyethylene glycol 1g/L, thiocarbamide 1g/L, Vanillin 1g/L, tonka bean camphor 1g/L.
Embodiment 5: coating surface has the shaped steel workpiece of Zn-Fe-praseodymium-promethium-europium-samarium coating, and coating is the Zn-Fe-praseodymium-promethium-europium-samarium composite deposite that contains zinc, iron and praseodymium, promethium, europium, samarium rare earth element.The thickness of coating is 17 * 10
-3Mm, the content range of various metallic elements is zinc 82% by weight in the coating, iron 11%, praseodymium 3%, promethium 1%, europium 2%, samarium 1%.
Zn-Fe-praseodymium-the promethium of this shaped steel-europium-samarium method for electroplating surface, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electrolytic solution again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from electrolytic solution.The pH value of electrolytic solution is 3.5, and galvanized current density is 5A/dm
2, temperature is room temperature, electroplating time is 2 hours.
This electrolytic solution be include chloride salt as the Fe of main salt and Zn, as the citric acid of Synergist S-421 95, as (the NH of conducting salt
4)
2SO
4, as the H of buffer reagent
3BO
3, and the electrolytic solution of praseodymium chloride, sulfuric acid promethium, europium sesquioxide, Samarium trioxide, it specifically consists of: FeCl
2180g/L, ZnCl
260g/L, (NH
4)
2SO
4110g/L, citric acid 30g/L, H
3BO
330g/L, xitix 0.9g/L, praseodymium chloride 6g/L, sulfuric acid promethium 2g/L, europium sesquioxide 4g/L, Samarium trioxide 2g/L, polyoxyethylene glycol 0.5g/L, thiocarbamide 1g/L Vanillin 0.5g/L, tonka bean camphor 1.5g/L.
Embodiment 6: coating surface has the shaped steel workpiece of Zn-Fe-neodymium-scandium-yttrium-cerium coating, and coating is the Zn-Fe-neodymium-scandium-yttrium-cerium composite deposite that contains zinc, iron and neodymium, scandium, yttrium, cerium mischmetal element.The thickness of coating is 16 * 10
-3Mm, the content range of various metallic elements is zinc 85% by weight in the coating, iron 10%, neodymium 1.5%, scandium 1.5%, yttrium 1%, cerium 1%.
Zn-Fe-neodymium-the scandium of this shaped steel-yttrium-cerium method for electroplating surface, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into plating tank electrolytic solution again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from electrolytic solution.The pH value of electrolytic solution is 4, and galvanized current density is 4A/dm
2, temperature is room temperature, electroplating time is 2 hours.
This electrolytic solution be include chloride salt as the Fe of main salt and Zn, as the citric acid of Synergist S-421 95, as (the NH of conducting salt
4)
2SO
4, as the H of buffer reagent
3BO
3, and the electrolytic solution of Neodymium trichloride, scandium sulfate, yttrium oxide, cerium oxide, it specifically consists of: FeCl
2170g/L, ZnCl
280g/L, (NH
4)
2SO
4100g/L, citric acid 30g/L, H
3BO
335g/L, xitix 0.9g/L, Neodymium trichloride 3g/L, scandium sulfate 3g/L, yttrium oxide 2g/L, cerium oxide 2g/L, polyoxyethylene glycol 0.5g/L, thiocarbamide 0.5g/L tonka bean camphor 1.5g/L.
Claims (4)
1, the coated iron and steel parts of a kind of coating surface, described coating is the Zn-Fe-RE composite deposite that contains zinc, iron and rare earth element, the content range that it is characterized in that the various metallic elements of described coating is zinc 78% to 88% by weight, iron 8% to 12%, rare earth element 0.5% to 10%.
2, a kind of iron and steel parts method for electroplating surface, be included in electroplate before to described component polish washing, oil removing, wash, remove corrosion then, after washing, put into the plating tank electroplate liquid again and carry out galvanized step, and the step of after electroplating, described iron and steel parts being taken out after washing, oven dry from plating bath, it is characterized in that consisting of of plating bath: FeCl
2100～200g/L, ZnCl
250～100g/L, (NH
4)
2SO
470～140g/L, citric acid 20～70g/L, H
3BO
320～40g/L, xitix 0.8～1.5g/L, rare-earth salts or rare earth oxide 1～20g/L, additive 0.5～5g/L.
3, electro-plating method according to claim 2 is characterized in that additive described in the plating bath is any or several arbitrary combination in polyoxyethylene glycol, thiocarbamide, Vanillin, the tonka bean camphor.
4, a kind of plating electrolytic solution is characterized in that consisting of of described electrolytic solution: FeCl
2100～200g/L, ZnCl
250～100g/L, (NH
4)
2SO
470～140g/L, citric acid 20～70g/L, H
3BO
320～40g/L, xitix 0.8～1.5g/L, rare-earth salts or rare earth oxide 1～20g/L, additive 0.5～5g/L.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100223082A CN1300382C (en) | 2004-04-12 | 2004-04-12 | Steel components and parts covered by Zn-Fe-RE cladding material, electroplating method and electrolyte |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100223082A CN1300382C (en) | 2004-04-12 | 2004-04-12 | Steel components and parts covered by Zn-Fe-RE cladding material, electroplating method and electrolyte |
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|---|---|
| CN1563503A CN1563503A (en) | 2005-01-12 |
| CN1300382C true CN1300382C (en) | 2007-02-14 |
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| CN105506715B (en) * | 2015-12-15 | 2017-11-03 | 东南大学 | A kind of preparation method of the composite mixed zinc coat of rare earth oxide graphene |
| CN110318077A (en) * | 2019-07-17 | 2019-10-11 | 安徽启明表面技术有限公司 | Non-cyanogen galvanization liquid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85106516A (en) * | 1984-12-03 | 1986-05-10 | 美国钢铁工程及顾问公司 | The galvanic deposit of zinc-iron alloys coating |
| JPH0466690A (en) * | 1990-07-04 | 1992-03-03 | Tokin Corp | Zinc-iron-group metal alloy plating bath and zinc-iron-group metal alloy plating method using the same |
| JP2000282255A (en) * | 1999-03-31 | 2000-10-10 | Nippon Hyomen Kagaku Kk | Metallic surface treating method |
| CN1480564A (en) * | 2003-07-18 | 2004-03-10 | 中山大学 | Method for preparing rare earth alloy through sweeping electric potential sedimentation |
| CN1485466A (en) * | 2002-09-27 | 2004-03-31 | 长沙高新技术产业开发区英才科技有限 | Process of electricity sedimentation in aqueous solution for producing rare earth magnetic film alloy material |
-
2004
- 2004-04-12 CN CNB2004100223082A patent/CN1300382C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85106516A (en) * | 1984-12-03 | 1986-05-10 | 美国钢铁工程及顾问公司 | The galvanic deposit of zinc-iron alloys coating |
| JPH0466690A (en) * | 1990-07-04 | 1992-03-03 | Tokin Corp | Zinc-iron-group metal alloy plating bath and zinc-iron-group metal alloy plating method using the same |
| JP2000282255A (en) * | 1999-03-31 | 2000-10-10 | Nippon Hyomen Kagaku Kk | Metallic surface treating method |
| CN1485466A (en) * | 2002-09-27 | 2004-03-31 | 长沙高新技术产业开发区英才科技有限 | Process of electricity sedimentation in aqueous solution for producing rare earth magnetic film alloy material |
| CN1480564A (en) * | 2003-07-18 | 2004-03-10 | 中山大学 | Method for preparing rare earth alloy through sweeping electric potential sedimentation |
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