CN106567059A - Pickling-free phosphating liquid and preparation method thereof - Google Patents
Pickling-free phosphating liquid and preparation method thereof Download PDFInfo
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- CN106567059A CN106567059A CN201610876730.7A CN201610876730A CN106567059A CN 106567059 A CN106567059 A CN 106567059A CN 201610876730 A CN201610876730 A CN 201610876730A CN 106567059 A CN106567059 A CN 106567059A
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- pickling
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- phosphating
- free phosphating
- phosphating liquid
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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
- C23C22/12—Orthophosphates containing zinc cations
- C23C22/13—Orthophosphates containing zinc cations containing also nitrate or nitrite anions
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- Mechanical Engineering (AREA)
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- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention belongs to the technical field of electrochemistry, and relates to a metal surface processing technology, in particular to pickling-free phosphating liquid and a preparation method thereof. The main component of the pickling-free phosphating liquid is a product generated through reaction of the following reactants including 10%-20% of zinc oxide, 5%-10% of ferric nitrate, 1%-5% of nickel nitrate, 35%-40% of phosphoric acid, 20%-30% of nitric acid and 10%-15% of water. According to the pickling-free phosphating liquid and the preparation method thereof, pretreatment before the phosphating process is conducted in the mode that on the basis that a wire coil shot blasting machine is adopted to conduct shot blasting cleaning, the preparation method of the pickling-free phosphating liquid is improved; by using the improved pickling-free phosphating liquid, phosphating film crystals formed on the surface of a machined workpiece are compact, uniform, fine and dense, a phosphating film is not prone to being disengaged, and meanwhile dust sticking and highlight phenomena do not occur on the surface of the phosphating film; and cracks caused by residual acid groups in gaps of the workpiece after pickling and occurring of corrosion are inhibited, and the corrosion resistance is achieved.
Description
Technical field
The present invention relates to technical field of electrochemistry, and in particular to metal surface treatment technology, a kind of nothing is further related to
Acid washing phosphorization liquid and its compound method.
Background technology
Phosphating process process is the process that a kind of chemistry and electrochemical reaction form phosphate chemical conversion film, is formed
Phosphate conversion film is referred to as phosphating coat.The purpose of phosphatization is mainly：Protection is provided to parent metal, is prevented to a certain extent
Metal is corroded；For front bottoming of painting, the adhesive force and anti-corrosion capability of paint film layer are improved；Rise in metal cold machining process
Antifriction lubrication is used.
Generally, bonderizing requires that surface of the work should be clean metal surface.Workpiece must enter before phosphatization
Row is except pretreatment such as oils and fatss, corrosion thing, oxide skin and surface adjustment.Before particularly painting, bottoming phosphatization also requires to make surface
Adjustment, makes metal surface possess certain " activity ", and forms in picturesque disorder unit cell substrate, could obtain uniform, careful, close
Real phosphating coat, reaches the requirement for improving paint film adhesion and corrosion resistance.Therefore, phosphatization pre-treatment is to obtain high-quality phosphatization
The basis of film, current phosphatization pre-treating method are mainly acid cleaning process method, and acid cleaning process is very big to Environmental Water pollution effect.
Pickling-free phosphating process selection mechanical removal of oxygen layer replaces chemical deoxidization layer, mechanical removal of oxygen layer equipment more than ten years
It is front just to have had mechanical manufacturer in research, there is the experiment that many producers have been also carried out many times, but all because phosphatization skill
Art corresponding problem：Film is kicked the beam 1～2g/m again2, phosphorization membrane easily comes off and counts out.
The content of the invention
It is in order to solve the above problems, of the invention on the basis of impeller blasting is carried out using disk unit shot-blasting machine, to pickling-free phosphorus
The compound method for changing liquid is improved.
The technical solution used in the present invention is：A kind of compound method of pickling-free phosphating liquid, it is characterized by according to following step
Suddenly complete：
(1) weigh according to following parts by weight or measure following raw materials according：
(2) Zinc Oxide weighed in step (1) is added into reactor, then the water for being measured is injected, be stirred；
(3) phosphoric acid measured in step (1) and nitric acid are injected separately in the reactor in step (1) and are stirred,
Material reacts in a kettle.；
(4) after above-mentioned reaction terminates, will be anti-in the ferric nitrate weighed in step (1), nickel nitrate implantation step (1)
In answering kettle, it is stirred；
(5) treat that temperature is cooled to room temperature, prepare a kind of pickling-free phosphating liquid.
The optimization of the present invention, according to a kind of compound method of pickling-free phosphating liquid described above, it is characterized by step (1)
Described in raw material weight percentage composition be：
The optimization of equipment used herein, a kind of compound method of the pickling-free phosphating liquid according to the top, its
It is characterized as described reactor inner surface acid corrosion-resistant.
Further optimization to the said equipment, according to a kind of compound method of pickling-free phosphating liquid described above, which is special
Levy for the reactor material be rustless steel, the reactor inner surface brushing acid-proof coating.
Using a kind of pickling-free phosphating liquid described in any of the above-described one compound method prepared by a kind of pickling-free phosphorus
Change liquid, it is characterized by the pickling-free phosphating liquid is liquid, the pickling-free phosphating liquid main component is by following reactants
The product that reaction is generated：Zinc Oxide, ferric nitrate, nickel nitrate, phosphoric acid, nitric acid, water；The weight of the pickling-free phosphating liquid reactant
Percentage composition is：
To a kind of further optimization of pickling-free phosphating liquid, according to a kind of pickling-free phosphating liquid described above, its feature
Weight percentage for the pickling-free phosphating liquid reactant is：
Compared with prior art, its effect is the present invention：Pretreatment of the present invention before phosphating process is using disk unit ball blast
On the basis of machine carries out impeller blasting, the compound method of pickling-free phosphating liquid is improved, the pickling-free phosphating liquid after improvement,
Phosphating coat compact crystallization that work piece surface formed, uniform, careful, closely knit is made, phosphating coat is difficult for drop-off, while phosphating coat table
Face without dust, highlight phenomenon generation, ask with suppressing workpiece to produce corrosion and slight crack occur because of residual acid group in gap after pickling
The appearance of topic, with corrosion resistance.
Specific embodiment
In order that the technological means of the present invention, creation characteristic, reached purpose and effect are easy to understand, in conjunction with concrete
Embodiment, is further elaborated to the present invention.
Embodiment one：A kind of compound method of pickling-free phosphating liquid, it is characterized by completing according to the following steps：
(1) weigh according to following parts by weight or measure following raw materials according：
Wherein Zinc Oxide 100g, ferric nitrate 100g, nickel nitrate 20g, 63% phosphoric acid 382ml, 98% nitric acid 204ml, water
140ml；
(2) Zinc Oxide weighed in step (1) is added into reactor, then the water for being measured is injected, be stirred；
(3) phosphoric acid measured in step (1) and nitric acid are injected separately in the reactor in step (1) and are stirred,
Material reacts in a kettle.；
(4) after above-mentioned reaction terminates, will be anti-in the ferric nitrate weighed in step (1), nickel nitrate implantation step (1)
In answering kettle, it is stirred；
(5) treat that temperature is cooled to room temperature, prepare a kind of pickling-free phosphating liquid.
A kind of reactor material used in the process for preparation of the film agent processed during wire rod is processed for cold plastic deformation
Matter is rustless steel, the acidproof chlorosulfonated polyethylene paint coating of the reactor inner surface brushing.
Embodiment two：A kind of compound method of pickling-free phosphating liquid, it is characterized by completing according to the following steps：
(1) weigh according to following parts by weight or measure following raw materials according：
Wherein Zinc Oxide 200g, ferric nitrate 50g, nickel nitrate 50g, 63% phosphatase 24 37ml, 98% nitric acid 136ml, water
100ml；
(2) Zinc Oxide weighed in step (1) is added into reactor, then the water for being measured is injected, be stirred；
(3) phosphoric acid measured in step (1) and nitric acid are injected separately in the reactor in step (1) and are stirred,
Material reacts in a kettle.；
(4) after above-mentioned reaction terminates, will be anti-in the ferric nitrate weighed in step (1), nickel nitrate implantation step (1)
In answering kettle, it is stirred；
(5) treat that temperature is cooled to room temperature, prepare a kind of pickling-free phosphating liquid.
A kind of reactor material used in the process for preparation of the film agent processed during wire rod is processed for cold plastic deformation
Matter is rustless steel, the reactor inner surface brushing vinyl lacquer of the resistance to peroxotungstic acid coating.
Embodiment three：A kind of compound method of pickling-free phosphating liquid, it is characterized by completing according to the following steps：
(1) weigh according to following parts by weight or measure following raw materials according：
Wherein Zinc Oxide 150g, ferric nitrate 60g, nickel nitrate 20g, 63% phosphatase 24 15ml, 98% nitric acid 170ml, water
140ml；
(2) Zinc Oxide weighed in step (1) is added into reactor, then the water for being measured is injected, be stirred；
(3) phosphoric acid measured in step (1) and nitric acid are injected separately in the reactor in step (1) and are stirred,
Material reacts in a kettle.；
(4) after above-mentioned reaction terminates, will be anti-in the ferric nitrate weighed in step (1), nickel nitrate implantation step (1)
In answering kettle, it is stirred；
(5) treat that temperature is cooled to room temperature, prepare a kind of pickling-free phosphating liquid.
A kind of reactor material used in the process for preparation of the film agent processed during wire rod is processed for cold plastic deformation
Matter is rustless steel, the reactor inner surface brushing phenolic acid resistance paint coating.
Respectively a kind of pickling-free phosphating liquid prepared by embodiment one, two, three is tested for phosphating process：
First, disk unit, wire rod are applied to
1st, the pretreatment of work piece surface：
(1) except oils and fatss --- impeller blasting：Impeller blasting is carried out using disk unit shot-blasting machine, the steel surface of workpiece is applied
With strength ball blast, oils and fatss thereon, rusty scale, welding slag and oxide skin are removed, is allowed to obtain the metallic luster of uniformity, to improve
The coating quality and antiseptic effect of steel.
(2) chemical washing：Soaked using trichloroethane or sprayed；
(3) wash：Soak in clean water or spray；
2nd, phosphating process：
(1) Phosphating Solution is prepared respectively according to embodiment one, two, three：This product is a kind of middle temperature zinc, ferrum, nickel series Phosphating Solution,
Take the phosphatization concentrated liquor prepared according to embodiment one, two, three and originally water volume ratio 1: 10, stirring, in acid resisting material system
Into treatment trough in be warming up to 40-50 DEG C, be sufficiently stirred for and be continuously heating to 55-75 DEG C, proceed by phosphating process.The product can
Processed iron and steel work piece surface is made to form that one layer of crystallization be thin and the phosphating coat of densification at short notice, film is in light grey to dark-grey
Color, phosphating coat fine uniform, anticorrosive wear-resistant performance are good；
(2) phosphating process temperature is 55-75 DEG C, and time control in 30-40 minutes, tremble up and down by timing in parkerizing process
Dynamic material frame, makes surface of the work clean, and reaction is uniform；Phosphorization film weight is more than 7.5g/m2.
(2) during use, tank liquor concentration constantly can decline, the phosphorating that do not stop concentrated liquor, maintain in treatment trough
The balance of total acidity and free acidity；Phosphatization concentrated liquor flow acceleration control free acidity FA be 1.0-2.5, total acidity
TA：15-25.
3rd, wash：1～2 road, room temperature are cleaned using spray or complete immersion water, the time is 0.5～1.0min.
4th, saponification：Saponification is carried out using sodium stearate.
5th, it is dried：Dry less than 180 DEG C.
The operation principle of above-mentioned phosphating process is：Phosphorization filming mechanism is simply stated with a chemical equation：
8Fe+5Me(H2PO4)2+8H2O→H3PO4-Me2Fe(PO4)2·4H2O (film)+Me3(PO4)·4H2O (film)+
7FeHPO4(sediment)+8H2↑
Me is Fe, Ni, Zn etc., and iron and steel is soaked in the pyrosol containing phosphoric acid and dihydric phosphate, will be formed with phosphorus
The grains phosphating coat of hydrochlorate precipitate composition, and produce one hydrogen ferrum sediment of phosphoric acid and hydrogen.This mechanism explains relatively rough,
Film forming procedure can not intactly be explained.Phosphorization filming process is mainly made up of following 4 steps：
1. sour etch reduces base metal surface H+ concentration
Fe-2e→Fe2+
2H2-+2e→2[H]+ (1)
2. accelerator (oxidant) accelerates
[O]+[H]→[R]+H2O
Fe2++[O]→Fe3++[R] (2)
In formula, [O] is accelerator (oxidant), and [R] is reduzate, is produced as accelerator oxidizes away first step reaction
Raw hydrogen atom, accelerates the speed of reaction (1), further results in metal surface H+ concentration and drastically declines.Simultaneously also by solution
In Fe2+It is oxidized into Fe3+。
3. the multistage dissociation of phosphate radical
H3PO4→H2PO4 -+H+→HPO4 2-+2H+→PO4 3-+3H- (3)
As the H+ concentration of metal surface drastically declines, cause phosphate radical ionic dissociation equilibrium at different levels to move right, be finally
PO4 3-。
4. calcium phosphate precipitation crystallization becomes phosphating coat
As the PO that metal surface dissociates4 3-Belong to the metal ion at interface (such as Zn with GOLD FROM PLATING SOLUTION2+、Ni+、Fe2+) reach it is molten
During degree product constant Ksp, calcium phosphate precipitation will be formed.
Zn2++Fe2++PO4 3-+H2O→Zn2Fe(PO4)2·4H2O↓ (4)
3Zn2++2PO4 3-+4H2O→Zn3(PO4)2·4H2O↓ (5)
Calcium phosphate precipitation forms phosphatization nucleus together with hydrone, and nucleus continues to grow up into phosphatization crystal grain, countless crystalline substances
Grain closely heaps metaphysics into phosphating coat.
The side reaction of calcium phosphate precipitation will form phosphating dregs
Fe3++PO4 3-→FePO4 (6)
Can be seen that from above mechanism：Appropriate oxidant can improve the speed of reaction (2)；Relatively low H+Concentration can make phosphorus
The ionic dissociation equilibrium of acid group dissociation reaction (3) is more easy to move right and dissociates PO4 3-；When such as there is activity and link work at selected spots with that in entire areas in metal surface,
Precipitation (4), (5) can be made to form calcium phosphate precipitation nucleus by being not required to too big supersaturation；The generation of phosphating dregs is depended on
In reaction (1) and reaction (2), Solution H+Concentration is high, and accelerator increases sediment by force.Accordingly, in actual phosphating formula and work
During skill is implemented：Appropriate stronger accelerator (oxidant)；Higher acid ratio (relatively low free acid, i.e. H+Concentration)；Make gold
Metal surface is adjusted to possess active site and can improve phosphating reaction speed, can fast filming at a lower temperature.It is heavy with regard to phosphatization
Slag.Because phosphating dregs are mainly FePO4, will accordingly reduce sediment weight must just reduce Fe3+Yield, i.e., by two
Method：Reduce the H of Phosphating Solution+Concentration (low free acidity)；Promoter concentration is reduced, to reduce Fe2+It is oxidized into Fe3+。
Zinc material is substantially identical with upper with aluminium phosphating mechanism.The phosphatization speed of zinc material, phosphating coat only have phosphoric acid zinc salt
Single composition, and sediment is little.Aluminium phosphatization will typically add more fluorine compounds, be allowed to form AlF3, AlF6 3-, aluminum
Material phosphatization step is poly- essentially identical with above-mentioned mechanism.
In medium temperature phosphating solution, due to containing a large amount of oxidized form accelerator, as long as tank liquor is not big load continuous operation, one
As will not produce Fe2+Overdosing problems, Fe2+Form iron phosphate sediment.
Ultimate principle, principal character and the advantages of the present invention of the present invention has been shown and described above.The technology of the industry
It should be appreciated that the present invention is not restricted to the described embodiments, the description in above-described embodiment and description is only the present invention to personnel
Preference, the present invention is not limited by above-mentioned preference, without departing from the spirit and scope of the present invention, of the invention
Can also there are various changes and modifications, these changes and improvements are both fallen within the scope of protection of present invention.
Although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
Understanding can carry out various changes, modification, replacement to these embodiments without departing from the principles and spirit of the present invention
And modification, the scope of the present invention be defined by the appended.
Claims (6)
1. a kind of compound method of pickling-free phosphating liquid, it is characterized by completing according to the following steps：
(1) weigh according to following parts by weight or measure following raw materials according：
(2) Zinc Oxide weighed in step (1) is added into reactor, then the water for being measured is injected, be stirred；
(3) phosphoric acid measured in step (1) and nitric acid are injected separately in the reactor in step (1) and are stirred, material
React in a kettle.；
(4) after above-mentioned reaction terminates, by the reactor in the ferric nitrate weighed in step (1), nickel nitrate implantation step (1)
In, it is stirred；
(5) treat that temperature is cooled to room temperature, prepare a kind of pickling-free phosphating liquid.
2. the compound method of a kind of pickling-free phosphating liquid according to claim 1, it is characterized by the original described in step (1)
Expect that weight percentage is：
3. the compound method of a kind of pickling-free phosphating liquid according to claim 1, it is characterized by table in described reactor
Face acid corrosion-resistant.
4. the compound method of a kind of pickling-free phosphating liquid according to claim 3, it is characterized by the reactor material is
Rustless steel, the reactor inner surface brushing acid-proof coating.
5. a kind of anacidity prepared by a kind of compound method of the pickling-free phosphating liquid according to claim 1-4 is arbitrary one
Phosphating Solution is washed, it is characterized by the pickling-free phosphating liquid is liquid, the pickling-free phosphating liquid main component is by following anti-
The product for answering thing reaction to generate：Zinc Oxide, ferric nitrate, nickel nitrate, phosphoric acid, nitric acid, water；The pickling-free phosphating liquid reactant
Weight percentage is：
6. a kind of pickling-free phosphating liquid according to claim 5, it is characterized by the weight of the pickling-free phosphating liquid reactant
Measuring percentage composition is：
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061626A (en) * | 1990-11-20 | 1992-06-03 | 新乡市东海配电设备厂 | A kind of new phosphide liquid and preparation method thereof |
| CN1434150A (en) * | 2002-01-25 | 2003-08-06 | 肖银华 | Method for preparing green environment protection type normal temp. liquid phosphide |
| CN102304708A (en) * | 2011-04-25 | 2012-01-04 | 大连三达奥克化学股份有限公司 | Signal detonator body deep-drawing phosphating agent and preparation method for signal detonator body deep-drawing phosphating agent |
| CN102304710A (en) * | 2011-04-25 | 2012-01-04 | 大连三达奥克化学股份有限公司 | Phosphating agent used before high-speed drawing of steel wires and preparation method for phosphating agent |
| CN104250762A (en) * | 2013-06-26 | 2014-12-31 | 无锡洛社科技创业有限公司 | Preparation method of oil injection pump plunger surface phosphating liquid |
-
2016
- 2016-10-08 CN CN201610876730.7A patent/CN106567059A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061626A (en) * | 1990-11-20 | 1992-06-03 | 新乡市东海配电设备厂 | A kind of new phosphide liquid and preparation method thereof |
| CN1434150A (en) * | 2002-01-25 | 2003-08-06 | 肖银华 | Method for preparing green environment protection type normal temp. liquid phosphide |
| CN102304708A (en) * | 2011-04-25 | 2012-01-04 | 大连三达奥克化学股份有限公司 | Signal detonator body deep-drawing phosphating agent and preparation method for signal detonator body deep-drawing phosphating agent |
| CN102304710A (en) * | 2011-04-25 | 2012-01-04 | 大连三达奥克化学股份有限公司 | Phosphating agent used before high-speed drawing of steel wires and preparation method for phosphating agent |
| CN104250762A (en) * | 2013-06-26 | 2014-12-31 | 无锡洛社科技创业有限公司 | Preparation method of oil injection pump plunger surface phosphating liquid |
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