CN109056034A - Room temperature electrolytic phosphating process and phosphating solution - Google Patents
Room temperature electrolytic phosphating process and phosphating solution Download PDFInfo
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- CN109056034A CN109056034A CN201810876649.8A CN201810876649A CN109056034A CN 109056034 A CN109056034 A CN 109056034A CN 201810876649 A CN201810876649 A CN 201810876649A CN 109056034 A CN109056034 A CN 109056034A
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- phosphating
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/36—Phosphatising
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Abstract
The invention discloses a kind of room temperature electrolytic phosphating process, the phosphating solution includes zinc ion, calcium ion, phosphate radical, nitrate anion, organic acid, nitroguanidine, and content is as follows: zinc ion: 10-63g/L；Calcium ion: 10-100g/L；Phosphate radical: 50-120g/L；Nitrate anion: 40-200g/L；Organic acid: 10-50g/L；Additive: 1-45g/L；Wherein phosphate radical is with P2O5Meter, phosphatization temperature is room temperature, applies 3-100A/dm by DC power supply2Electric current；Phosphatization temperature phosphating time 3-120 seconds；Phosphatization caudacoria weight is 8-20g/m2, drawing speed 4-10m/s, phosphatization temperature is room temperature, and is generated without phosphatization slag, is not necessarily to periodic cleaning electrode, does not have heavy metal in phosphating solution, meet environmental protection standard.
Description
[technical field]
Phosphorating treatment the present invention relates to metal wire material surface process field, before specially a kind of steel wire rod drawing.
[background technique]
Phosphorating treatment refers to metal containing handling in phosphatic solution, and metal surface is made to form phosphatization
Learn the process of conversion film.Over more than 100 years, phosphating coat be can be applied on the metal or alloy such as steel, aluminium, magnesium, can not only be mentioned
High corrosion-resistant, the adhesive force for improving matrix and coating, and the surface friction property of workpiece can be obviously improved, improve material
Cold-forming property.Hot-dipping galvanized coating layer has good ductility, and can react under certain condition with odium stearate
Zinc stearate film is generated, zinc stearate has excellent greasy property.Therefore Zinc phosphating technique is in wire drawing, trombone slide, deep-draw, cold
It is widely applied in the processing industries such as pier, improves wire drawing trombone slide speed, reduce mold damage.
Past more than 100 years, traditional phosphating process was general at present in the development and application of cold forming processing industry maturation
All over high temperature phosphating process is used, it is divided into immersion type and two kinds of on-line continuous formula.The latter's phosphatization speed is fast, production efficiency
Height, but in order to ensure phosphating time, Phosphating Slot is longer, reaches 20 meters or more, takes up a large area.Although high temperature phosphating process produces
Raw phosphatization film thickness, binding force is good, is able to satisfy the production of cold working industry at present, but energy consumption is high, and the phosphatization slag of generation is more.Mesh
It is preceding to have there is scholar how to begin one's study using phosphatization slag, however the suitable work of phosphatization slag is not found up to now, in industry
Industry processing mode is directly discharged in environment mainly using phosphatization slag as solid waste, this brings seriously to environment
Pollution.The energy is saved, reducing environmental pollution is the important research direction in phosphorization technology field.
Electrolytic phosphating process is since phosphating time is short, phosphatization temperature is low, and generation phosphatization slag is few, even without spies such as phosphatization slags
Point is paid close attention to by cold forming processing industry.International monopoly WO19980906A1 reports a kind of electrolytic phosphating liquid containing zinc and calcium
And its phosphating process, it forms while the phosphating coat of calcic and zinc, phosphating coat is thicker, reaches 40g/m2, but phosphating time is longer,
3 minutes are at least needed, so being not suitable for being applied to online fast bonderizing.Chinese patent 200610088638.0, which reports one kind, to be made
Make the quick electrolysis phosphating process of anode with zinc or iron, and auxiliary electrode is installed, forms phosphorus in the workpiece surface of certain shapes
Sour zinc film.But due to selecting zinc or iron to make anode, zinc or dissolved ferric iron are easy to produce zinc mud and phosphorus into processing bath in electrolytic process
Slugging not only generates solid slag, but also influences the stability of solution.
The matched electrolytic phosphating liquid of mechanical descaling requires to be heated to 50~60 DEG C, and phosphating solution concentration currently on the market
Height, total acid are up to 300 points, and phosphatization slag yield is big, almost just need within one month to clean one-time electrode.
It can be seen that providing the problem of a kind of improved etching solution is this field urgent need to resolve.
[summary of the invention]
The present invention is not necessarily to heavy metal in view of the above-mentioned problems, provide a kind of room temperature electrolytic phosphating process, more environmentally-friendly, and
Phosphating coat is porous, improves drawing speed.
To solve the above-mentioned problems, a kind of room temperature electrolytic phosphating process provided by the invention, the phosphating solution include zinc from
Son, calcium ion, phosphate radical, nitrate anion, organic acid, additive, content are as follows:
Zinc ion: 10-63g/L；
Calcium ion: 10-100g/L；
Phosphate radical: 50-120g/L；
Nitrate anion: 40-200g/L；
Organic acid: 10-50g/L；
Additive: 1-45g/L；
Wherein phosphate radical is with P2O5Meter, phosphatization temperature is room temperature, applies 3-100A/dm by DC power supply2Electric current；Phosphorus
Change temperature phosphating time 3-120 seconds；Phosphatization caudacoria weight is 8-20g/m2, drawing speed 4-10m/s, in the electrolytic phosphating liquid
Positive electrode and negative electrode are installed, anode selects surface to be coated with the titanium plate or titanium net of inert layer, and inert layer is at least one of platinum, iridium；
Cathode is the steel wire after phosphatization, and the additive is nitroguanidine.
Further, zinc ion is from least one of zinc, zinc oxide, zinc nitrate, zinc dihydrogen phosphate.
Further, phosphate anion is from zinc nitrate, calcium nitrate, phosphoric acid, sodium dihydrogen phosphate, zinc dihydrogen phosphate, phosphorus
At least one of acid dihydride potassium.
Further, calcium ion is from calcium nitrate.
Compared with prior art, the present invention has the advantage that
1. without phosphorus slugging generates, do not need periodic cleaning electrode, not only act as environmental-protection function, also save manpower and material resources at
This；
2. phosphatization temperature is room temperature, without heating, room temperature achieves that phosphorating treatment；
3. phosphatization speed is fast, most short 3s can form complete phosphating coat；
4. phosphating coat is cellular, convenient for carrier band lubricant, drawing speed is improved.
5. not needing heavy metal, cost is saved, also meets the requirement of discharge water quality, it is more environmentally-friendly.
[Detailed description of the invention]
Fig. 1 is SEM electron microscope photo scanning.
[specific embodiment]
One group or 0~20V of multiple groups adjustable DC power supply is selected to provide adjustable DC current.Anode selects surface plating
There are the titanium plate or titanium net of inert layer, inert layer can be the metal of the strong inerts such as platinum, iridium, using phosphating steel wire as cathode.For
Make homogeneous current distribution around steel wire, multiple power supplys can be used simultaneously, each power supply connects an anode, formed with steel wire
Multiple electrodes pair.Steel wire or wire rod after pickling, washing, table tune pre-treatment, different phosphatization formula of liquid is selected, according to room temperature
Quick electrolysis phosphating process carries out concrete operations, and specific implementation case is as follows:
Embodiment 1:
A kind of room temperature electrolytic phosphating liquid and phosphating process include zinc ion 55g/L, calcium ion 50g/ml, phosphate radical 80g/
L, nitrate anion 40g/L, organic acid 20g/L, nitroguanidine 45g/L, for the 70# steel wire of line footpath 8.0mm, phosphating time 3s, electric current
Density 100A/dm2, phosphatization caudacoria weight 15g/m2, drawing speed 6m/s, phosphating solution temperature is room temperature.
Embodiment 2:
A kind of room temperature electrolytic phosphating liquid and phosphating process, include zinc ion 32g/L, calcium ion 30g/L, phosphate radical 60g/L,
Nitrate anion 80g/L, organic acid 15g/L, nitroguanidine 22g/L, for the 70# steel wire of line footpath 6.5mm, phosphating time 30s, electric current is close
Spend 26A/dm2, phosphatization caudacoria weight 15g/m2, drawing speed 7m/s.
Embodiment 3:
A kind of room temperature electrolytic phosphating liquid and phosphating process, include zinc ion 40g/L, calcium ion 10g/L, phosphate radical 50g/L,
Nitrate anion 120g/L, organic acid 10g/L, nitroguanidine 1g/L, for the 70# steel wire of line footpath 3.0mm, phosphating time 120s, electric current
Density 3A/dm2, phosphatization caudacoria weight 8g/m2, drawing speed 10m/s.
Embodiment 4:
A kind of room temperature electrolytic phosphating liquid and phosphating process include zinc ion 63g/L, calcium ion 100g/L, phosphate radical 120g/
L, nitrate anion 95g/L, organic acid 42g/L, nitroguanidine 13g/L, for the 70# steel wire of line footpath 12.5mm, phosphating time 8s, electric current
Density 57A/dm2, phosphatization caudacoria weight 20g/m2, drawing speed 4m/s.
Embodiment 5:
A kind of room temperature electrolytic phosphating liquid and phosphating process include zinc ion 10g/L, calcium ion 80g/L, phosphate radical 100g/
L, nitrate anion 200g/L, organic acid 50g/L, nitroguanidine 5g/L, for the 70# steel wire of line footpath 5.5mm, phosphating time 8s, electric current
Density 85A/dm2, phosphatization caudacoria weight 10g/m2, drawing speed 8m/s.
In above-described embodiment, zinc ion is from least one of zinc, zinc oxide, zinc nitrate, zinc dihydrogen phosphate, phosphoric acid
Radical ion is with P2O5Meter, may come from zinc nitrate, calcium nitrate, phosphoric acid, sodium dihydrogen phosphate, zinc dihydrogen phosphate, in potassium dihydrogen phosphate
At least one, calcium ion is from calcium nitrate.
Organic acid may come from least one of citric acid, tartaric acid.
Service check:
Above-mentioned phosphating solution is used for follow on production testing, steel wire wire specification selects No. 70 high-carbon steel, line footpath 6.5mm, warp
Overpickling, washing, table tune, electrolytic phosphating, washing, saponification and baking process.After acid washing phosphorization after testing, electron spectrum
Analysis finds the ingredient of phosphating coat as conventional phosphatizing film, as shown in Figure 1, being lithoform, crystal uniform and smooth is porous,
Convenient for carrying lubricant, drawing speed is improved, high speed drawing is suitable for.Phosphorization film weight is detected according to GB-GB/T 9792-2003,
Film weighs to 10g/m2, meets suggestion of the Appendix D to cold forming mass area ratio is promoted in GB-T11376-1997.Most pass through afterwards
Wire drawing machine drawing is crossed, 4~10m/s of drawing speed, from the drawing of 6.5mm line footpath to 1.2mm, compression ratio reaches 95%, residual film weight 1g/
M2, surface color is normal, and wire-drawing die is normal, and 30 tons of continuous production or so, without phosphorus slugging in Phosphating Slot, phosphating solution is stablized.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped
Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should
It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art
The other embodiments being understood that.
Claims (4)
1. a kind of room temperature electrolytic phosphating process, it is characterised in that: the phosphating solution includes zinc ion, calcium ion, phosphate radical, nitric acid
Root, organic acid, additive, content are as follows:
Zinc ion: 10-63g/L；
Calcium ion: 10-100g/L；
Phosphate radical: 50-120g/L；
Nitrate anion: 40-200g/L；
Organic acid: 10-50g/L；
Additive: 1-45g/L；
Wherein phosphate radical is with P2O5Meter, phosphatization temperature is room temperature, applies 3-100A/dm by DC power supply2Electric current；Phosphatization temperature
Degree phosphating time 3-120 seconds；Phosphatization caudacoria weight is 8-20g/m2, drawing speed 4-10m/s, the interior installation of the electrolytic phosphating liquid
Positive electrode and negative electrode, anode select surface to be coated with the titanium plate or titanium net of inert layer, and inert layer is at least one of platinum, iridium；Cathode
For the steel wire after phosphatization, the additive is nitroguanidine.
2. room temperature electrolytic phosphating process according to claim 1, which is characterized in that zinc ion is from zinc, zinc oxide, nitre
At least one of sour zinc, zinc dihydrogen phosphate.
3. room temperature electrolytic phosphating process according to claim 1, which is characterized in that phosphate anion from zinc nitrate,
At least one of calcium nitrate, phosphoric acid, sodium dihydrogen phosphate, zinc dihydrogen phosphate, potassium dihydrogen phosphate.
4. room temperature electrolytic phosphating process according to claim 1, which is characterized in that calcium ion is from calcium nitrate.
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| CN201810876649.8A CN109056034A (en) | 2018-08-03 | 2018-08-03 | Room temperature electrolytic phosphating process and phosphating solution |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109468623A (en) * | 2018-12-29 | 2019-03-15 | 南京派诺金属表面处理技术有限公司 | Low slag, inexpensive high speed drawing phosphating solution and use technique |
| CN109778166A (en) * | 2019-03-25 | 2019-05-21 | 四川亨通兴达科技有限公司 | The phosphorization treatment process of phosphating solution, the preparation method of phosphating solution and metal wire rod |
| CN111455431A (en) * | 2020-05-15 | 2020-07-28 | 东莞市颖兴金属表面处理材料有限公司 | Preparation method of electrolytic phosphating solution |
| CN112064092A (en) * | 2020-09-15 | 2020-12-11 | 六安乐巴巴科技有限公司 | Method for phosphating surface of steel wire |
| CN112410769A (en) * | 2020-11-06 | 2021-02-26 | 南京派诺金属表面处理技术有限公司 | Phosphating solution for drawing and preparation method thereof |
| CN113073371A (en) * | 2021-03-22 | 2021-07-06 | 领润(南京)绿色化学有限公司 | Clean anode plate friendly electrolytic phosphating solution and phosphating process thereof |
| RU2791305C1 (en) * | 2022-12-17 | 2023-03-07 | федеральное государственное бюджетное образовательное учреждение высшего образования "Новгородский государственный университет имени Ярослава Мудрого" | Method of steel phosphating |
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| CN101892479A (en) * | 2010-07-15 | 2010-11-24 | 上海大学 | Aluminum alloy surface phosphatizing fluid and phosphatizing method |
| CN102418094A (en) * | 2011-11-16 | 2012-04-18 | 南京派诺金属表面处理技术有限公司 | Low-temperature phosphating concentrate and low-temperature phosphating technology for cold forming processing |
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| CN106757280A (en) * | 2016-12-13 | 2017-05-31 | 河南恒星钢缆股份有限公司 | A kind of low temperature On-line electrolytic dissolution Phosphating Solution |
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Patent Citations (5)
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| CN101892479A (en) * | 2010-07-15 | 2010-11-24 | 上海大学 | Aluminum alloy surface phosphatizing fluid and phosphatizing method |
| CN102418094A (en) * | 2011-11-16 | 2012-04-18 | 南京派诺金属表面处理技术有限公司 | Low-temperature phosphating concentrate and low-temperature phosphating technology for cold forming processing |
| CN103132122A (en) * | 2011-11-22 | 2013-06-05 | 吴怡岗 | Steel wire on-line normal-temperature electrolytic phosphatization method |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109468623A (en) * | 2018-12-29 | 2019-03-15 | 南京派诺金属表面处理技术有限公司 | Low slag, inexpensive high speed drawing phosphating solution and use technique |
| CN109778166A (en) * | 2019-03-25 | 2019-05-21 | 四川亨通兴达科技有限公司 | The phosphorization treatment process of phosphating solution, the preparation method of phosphating solution and metal wire rod |
| CN111455431A (en) * | 2020-05-15 | 2020-07-28 | 东莞市颖兴金属表面处理材料有限公司 | Preparation method of electrolytic phosphating solution |
| CN112064092A (en) * | 2020-09-15 | 2020-12-11 | 六安乐巴巴科技有限公司 | Method for phosphating surface of steel wire |
| CN112064092B (en) * | 2020-09-15 | 2023-03-28 | 六安乐巴巴科技有限公司 | Method for phosphating surface of steel wire |
| CN112410769A (en) * | 2020-11-06 | 2021-02-26 | 南京派诺金属表面处理技术有限公司 | Phosphating solution for drawing and preparation method thereof |
| CN113073371A (en) * | 2021-03-22 | 2021-07-06 | 领润(南京)绿色化学有限公司 | Clean anode plate friendly electrolytic phosphating solution and phosphating process thereof |
| RU2791305C1 (en) * | 2022-12-17 | 2023-03-07 | федеральное государственное бюджетное образовательное учреждение высшего образования "Новгородский государственный университет имени Ярослава Мудрого" | Method of steel phosphating |
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Application publication date: 20181221 |