CN104878372B - Phosphorizing liquid for pretreating high-carbon steel wire before drawing and preparation method of phosphorizing liquid - Google Patents
Phosphorizing liquid for pretreating high-carbon steel wire before drawing and preparation method of phosphorizing liquid Download PDFInfo
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- CN104878372B CN104878372B CN201510340575.2A CN201510340575A CN104878372B CN 104878372 B CN104878372 B CN 104878372B CN 201510340575 A CN201510340575 A CN 201510340575A CN 104878372 B CN104878372 B CN 104878372B
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Abstract
The invention discloses phosphorizing liquid for pretreating a high-carbon steel wire before drawing and a preparation method of the phosphorizing liquid.The phosphorizing liquid is prepared from phosphoric acid, zinc nitrate, zinc oxide, a compound as shown in formula I, and water; zinc oxide is added to little water and mixed into paste; then phosphoric acid is added and agitated; zinc nitrate and the compound as shown in formula I are added after phosphoric acid is dissolved; water is added until reaching the use height; then the heating ad agitating are performed, and the volume is fixed; the temperature in phosphorizing liquid preparation is controlled to be 65 to 75 DEG C; the prepared phosphorizing film is thick, uniform, dense, high in corrosion resistance, fast to form, and wide in applicable scope of the steel wire according to the specification.
Description
Technical field
The present invention relates to a kind of Phosphating Solution, more specifically, it relates to pre-process before a kind of drawing for high-carbon steel wire
Phosphating Solution and preparation method thereof.
Background technology
Steel wire is one of plate, pipe, type, the big kind of silk four of steel, be with gren rod Jing it is cold drawn made by reprocessing produce
Product.The master operation of Production for Steel Wire includes that raw material is selected, removes iron scale, drying, coating treatment, heat treatment, wire drawing, coating
Process etc..
Generally needed through phosphorating treatment before steel wire wire drawing, in particular for special steel and high-carbon steel, phosphorous chemical industry
Skill is an important link, and the purpose of phosphatization is to allow Steel Wire Surface to form phosphating coat, and phosphating coat surface energy effectively adsorbs profit
Lubrication prescription, so as to lubricant is brought into die hole during steel wire drawing, forms one layer effectively between steel wire and die hole
Lubrication mould, is easy to steel wire smoothly to deform stretching.And the existing steel wire phosphatization film thickness produced in Phosphating Solution phosphorating treatment compared with
Thin, film layer is loose easily to cause the excessive erosion of matrix, and the service life for causing steel wire rope is shortened, and is not suitable for different size
Steel wire, it is impracticable.
Phosphorating treatment makes necessary preamble treatment process before steel wire drawing, so-called phosphorating treatment refer to by steel wire with contain
, there is chemical reaction and form one layer in metal surface and stablize in the phosphoric acid hydrochloric acid solution contact of the metal ions such as zinc, manganese, calcium, iron
Insoluble phosphate layer chemical treatment method.The film for being formed is referred to as phosphating coat, and the tunic contributes to steel wire follow-up
Adsorb required lubricant in drawing process, and its own also has certain lubricity, while phosphating coat is also helped
In the antioxygenic property for improving steel wire, strengthen the Corrosion Protection of steel wire.It is most widely used in processing before steel wire drawing to be
Medium and high temperature zinc system and the phosphating process of zinc calcium system, need to be heated to certain temperature range by Phosphating Solution.Its energy consumption is big, repetition
Operation, sediment are more, environmental pollution is serious.
In order to overcome disadvantages mentioned above, low temperature and normal-temperance phosphating process are occurred in that, but its phosphating reaction speed is slow, needs
Substantial amounts of noble and unsullied property accelerator is added, phosphatization can just quickly carried out in low temperature.But this kind of accelerator is also easy to produce decomposition mostly
And toxic gas is discharged, the harm to environment is larger.Then electrolytic phosphating is occurred in that, it arranges one in phosphating pond and leads
Body, and using the conductor as anode, after applying electric current, there is electrification in the steel wire into Phosphating Solution as negative electrode in Steel Wire Surface
Learn reaction and form phosphating coat.Compared with traditional phosphorization technology, reducing the generation of sediment reduces the pollution to environment.It is existing
There are the following problems the electrolytic phosphating of technology：The phosphating coat that Steel Wire Surface is formed is in uneven thickness, and is difficult to control to phosphatization
Other reactions outside reaction occur, and Phosphating Solution goes bad.
The content of the invention
In view of the shortcomings of the prior art, it is an object of the invention to provide a kind of be used to locate in advance before high-carbon steel wire drawing
Phosphating Solution of reason and preparation method thereof causes the steel wire after phosphorating treatment to form thicker phosphating coat, and this phosphating coat is equal
Even densification, the corrosion resistance of film layer is strong, and phosphatization speed is fast, it is adaptable to the steel wire of different size.
For achieving the above object, the invention provides following technical scheme：One kind is for pretreatment before high-carbon steel wire drawing
Phosphating Solution, it is characterised in that its raw material is consisted of：
Compound of formula I is as follows：
Preferably, phosphoric acid 22g/L；Zinc nitrate 35g/L；Zinc oxide 26g/L；Compound of formula I 0.2g/L；Balance of water.
Preferably, phosphoric acid 25g/L；Zinc nitrate 42g/L；Zinc oxide 30g/L；Compound of formula I 0.3g/L；Balance of water.
Preferably, phosphoric acid 28g/L；Zinc nitrate 48g/L；Zinc oxide 34g/L；Compound of formula I 0.5g/L；Balance of water.
The preparation method of Phosphating Solution is pre-processed before a kind of described drawing for high-carbon steel wire, is comprised the following steps：
A, zinc oxide is added in a small amount of water, be tuned into pasty state；
B, add phosphoric acid and stir；
C, after phosphoric acid dissolving zinc nitrate and compound of formula I are added, added water to using height, heating stirring.
The pH of the Phosphating Solution is controlled 4～6, and Phosphating Solution temperature control is at 65～75 DEG C.
Described a kind of compound of formula I for Phosphating Solution, it is characterised in that represented with following formula：
Application of the described compound of formula I in terms of steel wire pretreatment.
Compared with prior art, it is an advantage of the current invention that：Reduce phosphating dregs, accelerate phosphatization speed in the composition of Phosphating Solution
The effect of degree and crystallization of refinement, secondly can improve the thickness of Steel Wire Surface phosphating coat, and film forming even compact, film layer corrosion resistant
Corrosion can be optimal, and nickel can occur displacement reaction and form galvanic cell in Steel Wire Surface with the iron of Steel Wire Surface, expand Steel Wire Surface cloudy
Pole scope, accelerates phosphating coat formation speed, and reduces the guarantee film forming even compact of the sulfate ion in Phosphating Solution, it is to avoid phosphorus
Change film loose and cause the excessive erosion of matrix, total acidity controlled during preparation with temperature in claimed range, film forming compared with
Thick even compact, adhesive force is high, contributes to the deformation wire drawing of steel wire.
Embodiment
Below by embodiment, the invention will be further described.It should be understood that embodiment of the present invention methods described
It is only used for the explanation present invention, rather than limitation of the present invention, to preparation side of the invention under the concept thereof of the present invention
The simple modifications of method belong to the scope of protection of present invention.The all raw materials used in embodiment and solvent are purchased from
Sigma Biochemical and Organic Compounds for Research and Diagnostic Clinical
Reagents companies.
Embodiment 1：
Phosphating Solution of the present invention is made up of following raw material：
Zinc oxide is added in a small amount of water, pasty state is tuned into, phosphoric acid is added, is stirred to fully dissolving.It is subsequently adding nitric acid
Zinc and compound of formula I, add water to using height, heating stirring constant volume.PH controls 4, temperature control at 65 DEG C, this kind of phosphorus
Change formula of liquid film forming speed is slower, and phosphating coat black is thicker, more loose, is suitable for the larger steel wire of specification.
Embodiment 2：
Phosphating Solution of the present invention is made up of following raw material：
Preparation method with embodiment 1, pH controls 5, temperature control at 70 DEG C, this kind of phosphatization formula of liquid phosphorization filming film forming
Speed is moderate, and phosphating coat black, thickness is moderate, closeer, and applicable wire gauge is wide.
Embodiment 3：
Preparation method with embodiment 1, pH controls 6, temperature control equally at 75 DEG C, this kind of Phosphating Solution phosphorization filming speed
Comparatively fast, phosphating coat grey black, relatively thin, fine and close, the less steel wire of applicable specification.
Embodiment 4：The preparation of compound of formula I
(1) 0.1 mole of 4- (4- iodophenyls) -4 '-propyl group bis cyclohexane is dissolved in the anhydrous THF of 100ml, is dropped with liquid nitrogen
Temperature under nitrogen protection, is slowly added dropwise the 2.5M n-BuLis-hexane solution into 10ml, stirring reaction 30 minutes to -80 DEG C
Afterwards, the solution that the trimethylborate into 3g is dissolved in THF is slowly added dropwise, stirring reaction is after 30 minutes, is raised to that reaction 1 is stirred at room temperature is little
When, the 6M diluted hydrochloric acid aqueous solutions of 150ml are added dropwise to, it is extracted with ethyl acetate, organic phase anhydrous sodium sulfate drying, filter, subtract
Pressure concentration is dry, adds the petroleum ether and stirring dispersion of 50ml, suction filtration to obtain white solid, without further purification directly into residue
Connect for next step reaction.
(2) 0.01 mole compound for obtaining (1st) step and 0.015 1- chlorine isoquinolin, the Anhydrous potassium carbonate of 3g,
The water mixing of the ethanol and 30ml of 100ml toluene and 50ml, adds the catalyst Pd (PPh of 115mg3)4, in nitrogen protection
Under, temperature rising reflux carries out coupling reaction 12 hours, is cooled to room temperature, separates organic phase, and water is mutually extracted with ethyl acetate, organic phase
It is dried, filters, filtrate reduced in volume is done, and residue over silica gel column separating purification obtains compound as white solid.
(3) 0.025 moles of (2nd) step compound and 0.02 NiCl3·3H2O be dispersed in 20ml ethylene glycol ethyl ether and
In 10ml water, under nitrogen protection, temperature rising reflux carries out substitution reaction 24 hours, is cooled to room temperature, filters, and filter cake is washed with water,
Vacuum drying, obtains the solid chemical compound of rufous.
1HNMR(6CDCl3)：0.81～0.98 (3H, m)；1.27～1.37 (2H, m)；1.50～1.59 (2H, m)；1.75
～1.91 (3H, m)；1.97～2.25 (16H, m)；2.62～2.80 (1H, m)；6.60～6.68 (2H, q)；6.99～7.02
(2H, t)；7.76～7.80 (2H, t)；8.25～8.36 (4H, m).
(4) acetylacetone,2,4-pentanedione of (3rd) step compound 0.1mmol and 0.35mmol and the natrium carbonicum calcinatum of 1.2mmol are taken
In being dispersed in the ethylene glycol ethyl ether of 20ml, under nitrogen protection, being warming up to 180 DEG C and being stirred at reflux carries out substitution reaction 24 hours,
Room temperature is cooled to, is filtered, filter cake is washed with water, then dissolved with DCM, filtered, filtrate is dried, filtered, filtrate reduced in volume is done, and obtains
Dark red solid compound.
1HNMR(6CDCl3)：0.80～1.45 (13H, m)；1.51～1.88 (8H, m)；5.76 (1H, s)；7.40～
7.45 (3H, m)；7.61～7.90 (3H, m)；8.08～8.25 (3H, m).
Comparing embodiment 1：
Method according to embodiment 1 is prepared, but without compound of formula I.
Application Example：
Using 70#Steel wire is determined the experiment of rust cleaning rate.By steel wire respectively with embodiment 1 and the phosphorus of comparing embodiment 1
Change liquid to process.Steel wire is cut into into 10em length, and is rubbed using sand paper.Then steel wire is placed in salt fog cabinet (ASTM B117) and is protected
Hold 48 hours so that it rusty scale occurs.
Using concentrated hydrochloric acid, then the steel wire for processing is immersed in 5 minutes in concentrated hydrochloric acid.
Rust cleaning rate (%) is represented with equation below：
Wherein：
A=is stained with weight (g) of the steel wire of iron rust before rust cleaning；
B=steel wires are being eliminated rust with rust remover, washed with water and dried weight (g)；
Weight (g) of the c=steel wires before getting rusty.
The value of rust cleaning rate is higher, and the effect of rust cleaning is better.
In Corrosion protection grade experiment, using X-rite8400 colour examining spectrophotometer (ASTM standard D1003 turbidity and transmission
Coefficient determination method) corrosion is estimated.In this experiment, daylight is used as into light source and compares L value (L：The brightness of color, a：
Green-the red value of color, and b：The blue-yellow value of color；A and b) is not compared herein.L values are less, through salt fog cabinet
The steel wire color of process is darker, so as to show that extent of corrosion is bigger.L ＜ 50 represent heavy corrosion, and 50 ＜ L ＜ 60 represent corrosion,
60 ＜ L ＜ 75 represent mild corrosion, and 75 ＜ L represent no corrosion.
Performance detection：
The steel wire that embodiment 1 and comparing embodiment 1 were processed carries out together rust cleaning detection, and acquired results are as follows：
| The steel wire of the Phosphating Solution of embodiment 1 process | The steel wire of the Phosphating Solution of comparing embodiment 1 process | |
| Rust cleaning rate | 20 | 55 |
| L values | 85 | 59 |
As can be seen from the above table, using strong inorganic acid, such as hydrochloric acid is eliminated rust, at the Phosphating Solution using comparing embodiment 1
The steel wire of reason is through hydrochloride derusting, and gained rust amount is more, illustrates seriously corroded, and through the steel that processes of Phosphating Solution of embodiment 1
, through hydrochloride derusting, gained rust amount is less, illustrates no corrosion for silk；By the contrast of L values it can also be seen that through embodiment
The steel wire no corrosion of 1 Phosphating Solution process.
The above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned enforcement
Example, all technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It should be pointed out that for the art
Those of ordinary skill for, some improvements and modifications without departing from the principles of the present invention, these improvements and modifications
Should be regarded as protection scope of the present invention.
Claims (7)
1. the Phosphating Solution for pre-processing before a kind of drawing for high-carbon steel wire, it is characterised in that its raw material is consisted of：
Balance of water；
Compound of formula I is as follows：
2. Phosphating Solution according to claim 1, it is characterised in that its raw material is consisted of：Phosphoric acid 22g/L；Zinc nitrate 35g/L；
Zinc oxide 26g/L；Compound of formula I 0.2g/L；Balance of water.
3. Phosphating Solution according to claim 1, it is characterised in that its raw material is consisted of：Phosphoric acid 25g/L；Zinc nitrate 42g/L；
Zinc oxide 30g/L；Compound of formula I 0.3g/L；Balance of water.
4. Phosphating Solution according to claim 1, it is characterised in that its raw material is consisted of：Phosphoric acid 28g/L；Zinc nitrate 48g/L；
Zinc oxide 34g/L；Compound of formula I 0.5g/L；Balance of water.
5. the preparation method of Phosphating Solution, its feature are pre-processed before a kind of drawing for high-carbon steel wire according to claim 1
It is to comprise the following steps：
A, zinc oxide is added in a small amount of water, be tuned into pasty state；
B, add phosphoric acid and stir；
C, after phosphoric acid dissolving zinc nitrate and compound of formula I are added, added water to using height, heating stirring；
The pH of the Phosphating Solution is controlled 4～6, and Phosphating Solution temperature control is at 65～75 DEG C.
6. a kind of compound of formula I for Phosphating Solution, it is characterised in that represented with following formula：
7. application of the compound of formula I described in claim 6 in terms of steel wire pretreatment.
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| CN201510340575.2A CN104878372B (en) | 2015-06-18 | 2015-06-18 | Phosphorizing liquid for pretreating high-carbon steel wire before drawing and preparation method of phosphorizing liquid |
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| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101063200A (en) * | 2006-04-24 | 2007-10-31 | 宋晨玮 | Normal temperature phosphating liquor |
| CN103422082A (en) * | 2012-05-17 | 2013-12-04 | 中化化工科学技术研究总院 | Neodymium-iron-boron magnetic material zinc-series phosphatization liquid and application method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101063200A (en) * | 2006-04-24 | 2007-10-31 | 宋晨玮 | Normal temperature phosphating liquor |
| CN103422082A (en) * | 2012-05-17 | 2013-12-04 | 中化化工科学技术研究总院 | Neodymium-iron-boron magnetic material zinc-series phosphatization liquid and application method thereof |
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