阅读说明：本技术 一种钢丝生产工艺以及制备的钢丝 (Steel wire production process and prepared steel wire ) 是由 王志永 李鹏 张延旭 于 2021-08-16 设计创作，主要内容包括：本申请公开了一种钢丝生产工艺以及制备的钢丝,所述钢丝的生产工艺,包括以下步骤：S1：对盘条进行热处理；S2：盘条酸洗后喷涂草酸锰溶液,在220～250℃的温度下烘干；S3：采用过氧化氢水溶液浸泡盘条；S4：采用磷化液进行对盘条进行磷化处理；所述磷化原液稀释5～15倍,得到磷化液,磷化液调节pH为3～5；所述磷化原液包括以下质量份的原料制得：氧化锌：8～25份、硝酸镍：2～6份、硝酸钠：2～8份、磷酸：4～8份、亚硝酸钠：0.1～0.3份；S5：盘条拉丝处理；S6：对钢丝进行锌铝合金镀层；S7：再次对钢丝进行热处理。得到的成品钢丝磷化膜致密程度高、磷化膜表面光滑,钢丝与锌铝合金镀层结合程度高。(The application discloses steel wire production technology and steel wire of preparation, steel wire's production technology includes following step: s1: carrying out heat treatment on the wire rod; s2: after pickling, spraying a manganese oxalate solution on the wire rod, and drying at 220-250 ℃; s3: soaking the wire rod in aqueous hydrogen peroxide solution; s4: phosphating the wire rod by using a phosphating solution; diluting the phosphating stock solution by 5-15 times to obtain a phosphating solution, and adjusting the pH value of the phosphating solution to 3-5; the phosphating stock solution is prepared from the following raw materials in parts by mass: zinc oxide: 8-25 parts of nickel nitrate: 2-6 parts of sodium nitrate: 2-8 parts of phosphoric acid: 4-8 parts of sodium nitrite: 0.1-0.3 part; s5: wire rod drawing treatment; s6: carrying out zinc-aluminum alloy coating on the steel wire; s7: the steel wire is heat treated again. The obtained finished steel wire phosphating film has high compactness, smooth surface and high combination degree of the steel wire and the zinc-aluminum alloy coating.)

1. A production process of a steel wire is characterized by comprising the following steps:

the method comprises the following steps:

s1: stabilizing the wire rod, wherein the stabilizing treatment is heat treatment to obtain a heat-treated wire rod;

s2: pickling the heat-treated wire rod, spraying a manganese oxalate solution after pickling, drying the acid-treated wire rod at 220-250 ℃ to obtain a pretreated wire rod, wherein the concentration of manganese oxalate in a manganese oxalate solution is 0.1-0.5 mmol/L;

s3: soaking the pretreated wire rod in aqueous hydrogen peroxide solution for 20-25 min, wherein the concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution is 0.1-1.4 mmol/L, so as to obtain a repaired wire rod;

s4: phosphating the repaired wire rod by adopting phosphating solution to obtain a phosphated wire rod,

the phosphating solution is obtained by diluting a phosphating stock solution and adjusting the pH value, wherein the dilution ratio of the phosphating stock solution is 1: 15-1: 5, regulating the pH value of the phosphating solution to 3-5;

the phosphating stock solution is prepared from the following raw materials in parts by mass:

zinc oxide: 8 to 25 portions of,

Nickel nitrate: 2 to 6 parts of,

Sodium nitrate: 2 to 8 parts of,

Phosphoric acid: 4 to 8 portions of,

Sodium nitrite: 0.1 to 0.3 part,

S5: carrying out wire drawing treatment on the phosphated wire rod, and carrying out continuous drawing for nine times to obtain a plain steel wire;

s6: carrying out zinc-aluminum alloy coating on the plain steel wire to obtain a coated steel wire;

s7: and stabilizing the plated steel wire again to obtain a finished steel wire.

2. A process for the production of a steel wire according to claim 1, characterized in that: and adjusting the pH value of the phosphating solution to 3-4.

3. A process for the production of a steel wire according to claim 1, characterized in that: the concentration of hydrogen peroxide in the hydrogen peroxide aqueous solution is 0.2 mmol/L-1 mmol/L.

4. A process for the production of a steel wire according to claim 1, characterized in that: the concentration of the manganese oxalate in the manganese oxalate solution is 0.2 mmol-0.4 mmol/L.

5. A process for the production of a steel wire according to claim 1, characterized in that: the concentration of sodium nitrite in the phosphating solution is 1 mmol-5 mmol/L.

6. A process for the production of a steel wire according to claim 1, characterized in that: the zinc-aluminum alloy coating is plated in a hot-dip mode.

7. A process for the production of a steel wire according to claim 6, wherein: the thickness of the coating is 300g/m²~350g/m²。

8. A steel wire characterized by: the steel wire is prepared by the steel wire production process of any one of claims 1 to 6.

9. A steel wire according to claim 8, characterized in that: the steel wire comprises a plating layer and a steel wire body, and the steel wire comprises the following components: c (0.8-1.2 wt%), S (0.01-0.03 wt%), P (0.01-0.03 wt%), Cu (0.20-0.40 wt%), Cr (0.20-0.40 wt%), Ni (0.10-0.20 wt%), Mn (0.20-0.40 wt%), and the balance of Fe and inevitable impurities.

Technical Field

The application relates to the technical field of building materials, in particular to a steel wire production process and a prepared steel wire.

Background

The steel wire is one of four major varieties of steel plate, pipe, mould and wire, and is a reprocessed product made by cold drawing hot rolled wire rod. Steel wire is generally produced by the following steps: selecting raw materials, removing iron scale, drying, phosphorizing, drawing wire, plating a coating, stabilizing treatment and the like.

In order to increase the corrosion resistance and wear resistance of the steel wire, a plating layer is plated on the surface of the steel wire during the processing of the steel wire, and in order to make the plating layer and the steel wire more tightly combined, a phosphating treatment is generally adopted as a pretreatment of coating. After a steel wire is treated with a solution containing phosphates such as zinc, manganese, chromium, iron, etc., an insoluble phosphate film with good adhesion is formed on the surface of the steel wire, and a process of forming a phosphate film is called phosphating.

The existing phosphating solution and a steel wire react to form a phosphating film with insufficient compactness, and in order to improve the compactness, the thickness of the phosphating film is generally improved by adopting a mode of improving the concentration of the phosphating solution and increasing the phosphating time, so that the compactness of the phosphating film is improved. Increasing the concentration of the phosphating film, while increasing the densification of the phosphating film, also brings about problems, such as: high production cost, difficult treatment of later-stage phosphating solution and the like; the increase of the phosphating time of the phosphating film can also increase the compactness of the phosphating film, but can cause low production efficiency of the steel wire. In addition, the phosphating process also has a phosphating defect, and the phosphating defect is that impurities on the surface of the steel wire are formed into a film in the phosphating process, and the impurities are wrapped by a phosphating film, so that the phosphating film is uneven, burrs and particles appear, and the problem of impurity film formation on the surface of the steel wire cannot be solved by improving the concentration of phosphating solution and increasing the phosphating time.

Disclosure of Invention

In order to improve the defect that the compact degree of a phosphating film is not enough and burrs and particles are generated in the phosphating process in the steel wire preparation process, the application provides a steel wire production process and a prepared steel wire.

In a first aspect, the steel wire production process provided by the application adopts the following technical scheme:

a production process of a steel wire comprises the following steps:

s1: stabilizing the wire rod, wherein the stabilizing treatment is heat treatment to obtain a heat-treated wire rod;

s2: pickling the heat-treated wire rod, spraying a manganese oxalate solution after pickling, drying the acid-treated wire rod at 220-250 ℃ to obtain a pretreated wire rod, wherein the concentration of manganese oxalate in a manganese oxalate solution is 0.1-0.5 mmol/L;

s3: soaking the pretreated wire rod in aqueous hydrogen peroxide solution for 20-25 min, wherein the concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution is 0.1-1.4 mmol/L, so as to obtain a repaired wire rod;

s4: phosphating the repaired wire rod by adopting phosphating solution to obtain a phosphated wire rod,

the phosphating solution is obtained by diluting a phosphating stock solution and adjusting the pH value, wherein the dilution ratio of the phosphating stock solution is 1: 15-1: 5, regulating the pH value of the phosphating solution to 3-5;

the phosphating stock solution is prepared from the following raw materials in parts by mass:

zinc oxide: 8 to 25 portions of,

Nickel nitrate: 2 to 6 parts of,

Sodium nitrate: 2 to 8 parts of,

Phosphoric acid: 4 to 8 portions of,

Sodium nitrite: 0.1 to 0.5 part,

S5: carrying out wire drawing treatment on the phosphated wire rod, and carrying out continuous drawing for nine times to obtain a plain steel wire;

s6: carrying out zinc-aluminum alloy coating on the plain steel wire to obtain a coated steel wire;

s7: and stabilizing the plated steel wire again to obtain a finished steel wire.

Through above-mentioned technical scheme, this application obtains the finished steel wire after carrying out wire drawing, plating coat and stabilizing treatment to the wire rod after the bonderizing, if bonderizing film density is not enough among the bonderizing process, the bonderizing produces the defect and can produce the influence to follow-up step, this application can improve the density of bonderizing film when solving the bonderizing defect. This application does not increase bonderizing time and bonderizing concentration, can reduce the possibility that impurity is wrapped up by the phosphating coat, realizes high-speed bonderizing process simultaneously.

The hydrogen peroxide has strong oxidizing property, and can oxidize burrs and surface defects on the surface of the steel wire to make the surface of the steel wire smooth and achieve the effect of adjustment;

however, a single hydrogen peroxide oxidation adjustment requires a high concentration (8% by mass or more), and the high concentration hydrogen peroxide is strongly self-decomposed, so that it is not practical to realize a high concentration;

on the other hand, low concentrations of hydrogen peroxide (0.2% by mass or less) can still be oxidatively adjusted, but the rate of oxidation adjustment is slow and the time is long;

therefore, hydrogen peroxide with specific concentration is combined with manganese oxalate, a manganese oxalate solution is sprayed on the surface of the steel wire after being washed by acid, and is dried at the temperature of 220-250 ℃, manganese oxalate is decomposed into manganese oxide, the activation energy of peroxide bonds can be improved in manganese oxide, the oxidation of iron in the surface of the steel wire by the hydrogen peroxide is promoted, the efficiency of the oxidation of the iron by the iron peroxide is improved, and the effect of adjusting the surface of the steel wire by the low-concentration hydrogen peroxide is realized. During the surface conditioning process, iron is oxidized to iron hydroxide, and the remaining manganese oxide is wrapped by the iron hydroxide and adheres to the surface of the steel wire.

And (3) putting the steel wire into the phosphating solution, decomposing ferric hydroxide in an acid solution, and combining ferric ions and phosphate radicals in the phosphating solution to form insoluble ferric phosphate precipitate so as to promote the phosphating process. Manganese oxide dissolved in phosphating solution after decomposition of ferric hydroxide, Mn²⁺Mn diffusing out from the surface of the steel wire²⁺Mn on the surface of the steel wire by concentration difference in the phosphating solution²⁺Higher concentration of Mn²⁺Has good depolarization effect on the phosphorization process and promotes the progress of the phosphorization reaction.

Optionally, the pH of the diluted phosphating solution is 3-4.

Through the technical scheme, when the acidity in the phosphating solution is too high, the corrosion reaction on the surface of the steel part is too fast, and bubbles generated by the reaction are too much to hinder the formation of a phosphating film. When the speed in the phosphating solution is too low, the corrosion is slow, and a phosphating film is difficult to form.

Optionally, the concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution is 0.2mmol/L to 1 mmol/L.

Through the technical scheme, the concentration of the hydrogen peroxide in the hydrogen peroxide aqueous solution is 0.2 mmol/L-1 mmol/L, the hydrogen peroxide with higher concentration can be violently decomposed by self, the hydrogen peroxide with low concentration can be still subjected to oxidation adjustment, but the oxidation adjustment speed is slow and the time is long.

Optionally, the concentration of manganese oxalate in the manganese oxalate solution is 0.2mmol/L to 0.4 mmol/L.

Through the technical scheme, the concentration of the manganese oxalate is 0.2 mmol-0.4 mmol/L, the high-concentration manganese oxalate is oxidized into the high-concentration manganese oxide, the self-decomposition of the hydrogen peroxide is promoted when the concentration of the manganese oxide is too high, and the oxidation reaction of the hydrogen peroxide is difficult to promote when the concentration of the manganese oxide is too low.

Optionally, the concentration of sodium nitrite in the phosphating solution is 1mmol/L to 5 mmol/L.

Through the technical scheme, sodium nitrite is a good phosphating reaction accelerator, excessive consumption of zinc salt can occur when the sodium nitrite is excessively added, the metal surface is passivated, a good phosphating film is difficult to generate, and the effect of promoting phosphating is difficult to play when the sodium nitrite is excessively added.

Optionally, the zinc-aluminum alloy coating is plated in a hot-dip mode.

Through the technical scheme, the hot-dip galvanized aluminum alloy has strong toughness, good reliability and durability of the coating.

Optionally, the plating thickness is 300g/m²～350g/m²。

Through the technical scheme, the excessively thick plating layer can cause the appearance of the plating layer to be rough and easy to peel off, and the steel grating plated part cannot be collided in the carrying and mounting processes; an excessively thin plating layer is difficult to play a role in protecting the steel wire.

In a second aspect, the present application provides a steel wire that adopts the following technical scheme:

alternatively, a steel wire, prepared by the above steel wire production process.

Optionally, the steel wire comprises the following components of C (0.8-1.2 wt%), S (0.01-0.03 wt%), P (0.01-0.03 wt%), Cu (0.20-0.40 wt%), Cr (0.20-0.40 wt%), Ni (0.10-0.20 wt%), Mn (0.20-0.40 wt%), and the balance of Fe and inevitable impurities.

In summary, the present application provides at least one of the following advantages:

1. this application can improve the density of bonderizing membrane when solving the bonderizing defect. Hydrogen peroxide can be to steel wire surface burr, surface defect department adjusts, hydrogen peroxide concentration crosses lowly too high and all can bring adverse effect to steel wire surface adjustment, so adopt specific concentration's hydrogen peroxide to combine the manganese oxalate of this application in this application, spout manganese oxalate solution on the steel wire surface after the pickling, it is dry under 220~250 ℃ of temperature, manganese oxalate decomposes into manganese oxide, can improve the activation energy of peroxide bond in the manganese oxide, promote the iron in the hydrogen peroxide oxidation steel wire surface, improve the efficiency of hydrogen peroxide oxidation iron, realize the effect that low concentration's hydrogen peroxide adjusted the steel wire surface. In the surface conditioning process, iron is oxidized into ferric hydroxide, and the remaining manganese oxide is wrapped by the ferric hydroxide and attached to the surface of the steel wire;

and (3) putting the steel wire into the phosphating solution, decomposing ferric hydroxide in an acid solution, and combining ferric ions and phosphate radicals in the phosphating solution to form insoluble ferric phosphate precipitate so as to promote the phosphating process. Manganese oxide dissolved in phosphating solution, Mn²⁺Mn diffusing out from the surface of the steel wire²⁺Mn on the surface of the steel wire by concentration difference in the phosphating solution²⁺Higher concentration of Mn²⁺The method plays a good depolarization role in the phosphating process and promotes the progress of the phosphating reaction;

2. when the acidity in the phosphating solution is too high, the corrosion reaction on the surface of the steel part is too fast, and too many bubbles are generated by the reaction, so that the formation of a phosphating film is hindered. When the speed in the phosphating solution is too low, the corrosion is slow, and a phosphating film is difficult to form.

Detailed Description

Preparation example 1

A phosphating stock solution is prepared by mixing the following raw materials in parts by mass:

zinc oxide: 9 parts of nickel nitrate: 5 parts, sodium nitrate: 7 parts of phosphoric acid: 5 parts, sodium nitrite: 0.1 part and 50 parts of water.

Preparation example 2

A phosphating stock solution is prepared by mixing the following raw materials in parts by mass:

zinc oxide: 9 parts of nickel nitrate: 5 parts, sodium nitrate: 7 parts of phosphoric acid: 5 parts, sodium nitrite: 0.25 part and 50 parts of water.

Preparation example 3

A phosphating stock solution is prepared by mixing the following raw materials in parts by mass:

zinc oxide: 9 parts of nickel nitrate: 5 parts, sodium nitrate: 7 parts of phosphoric acid: 5 parts, sodium nitrite: 0.5 part and 50 parts of water.

Example 1

A production process of a steel wire comprises the following steps:

s1: carrying out heat treatment on the wire rod, wherein the stabilizing treatment is heat treatment, the treatment temperature is 955 ℃, and the treatment time is 25min, so as to obtain a heat-treated wire rod;

s2: pickling the heat-treated wire rod by using 0.05mol/L dilute sulfuric acid for 15min, and spraying a manganese oxalate solution after pickling, wherein the concentration of manganese oxalate in the manganese oxalate solution is 0.5mmol/L, and the spraying amount is 3g/m²Drying at 230 ℃ after spraying to obtain a pretreated wire rod;

s3: soaking the pretreated wire rod in aqueous hydrogen peroxide solution for 25min, wherein the concentration of hydrogen peroxide in the aqueous hydrogen peroxide solution is 0.8mmol/L, so as to obtain a repaired wire rod;

s3: phosphating the repaired wire rod by using phosphating solution for 10min to obtain a phosphated wire rod; the phosphating solution is prepared by adopting the phosphating stock solution of preparation example 1, diluting according to the dilution ratio of 1:10 and adjusting the pH value to 4;

s4: carrying out wire drawing treatment on the phosphatized wire rod by using a wire drawing die, wherein the working cone angle of the wire drawing die is 10 degrees, the length of a die core is 35mm, the tension is 80000N, nine times of continuous drawing are carried out to obtain a plain steel wire, and the measured diameter is 7 mm;

s5: hot galvanizing aluminium alloy is carried out on the smooth steel wire to obtain a coated steel wire, and the coating thickness is 300g/m²；

S6: and (3) carrying out stabilizing heat treatment on the plated steel wire at the treatment temperature of 955 ℃ to obtain a finished steel wire.

Examples 2 to 5

A steel wire preparation process is based on example 2, and is characterized in that process parameters are different, and specific process parameters are shown in Table 1.

TABLE 1 Process parameters for examples 1-5 and comparative examples 1-3

Uniformly mixing an adhesive according to the ratio of 1:1 of resin to a curing agent, uniformly coating the mixture on the surface of a clean spindle without a paint layer, bonding a test column surface with a coating sample to be tested through the adhesive, curing the mixture for 16 hours at 40 ℃, treating the periphery of the test column by using a cutting device until the periphery is cut through to a substrate, and pulling the test sample and the coating apart by using a digital display pull-open method adhesion tester at the speed of not more than 1MPa/s within 90s to obtain the adhesion between the coating and the substrate, wherein the adhesion tests of different embodiments are shown in the following table.

TABLE 2 adhesion test for examples 1 to 5 and comparative examples 1 to 3

Compared with the comparative example 1, the manganese oxalate is added before the surface of the steel wire is finished, so that the binding power between the steel wire and the zinc-aluminum coating is improved.

Compared with the comparative example 2, the example 2 has the advantage that the adhesion between the steel wire and the zinc-aluminum coating is improved by adding hydrogen peroxide during the surface adjustment of the steel wire.

Compared with the example 2, the comparative example 1 and the comparative example 2, the comparative example 3 adds the hydrogen peroxide and the manganese oxalate, and the hydrogen peroxide and the manganese oxalate have synergistic action, so that the binding force between the steel wire and the zinc-aluminum coating is improved.

Examples 6 to 13

A steel wire preparation process is based on example 2, and is characterized in that process parameters are different, and specific process parameters are shown in Table 3.

Specific process parameters for examples 6-13 are shown in Table 3.

TABLE 3 Process parameters for examples 6 to 13

Uniformly mixing an adhesive according to the ratio of 1:1 of resin to a curing agent, uniformly coating the mixture on the surface of a clean spindle without a paint layer, bonding a test column surface with a coating sample to be tested through the adhesive, curing the mixture for 16 hours at 40 ℃, treating the periphery of the test column by using a cutting device until the periphery is cut through to a substrate, and pulling the test sample and the coating apart by using a digital display pull-open method adhesion tester at the speed of not more than 1MPa/s within 90s to obtain the adhesion between the coating and the substrate, wherein the adhesion tests of different embodiments are shown in the following table.

TABLE 4 adhesion test for examples 6-13

In examples 6 to 7 of the present application, the pH of the phosphating solution was adjusted, and the larger the pH value was, the worse the adhesion between the steel wire and the zinc-aluminum plating layer was, in the range of 3 to 5, as compared with example 2.

In the embodiments 8 to 11 of the present application, hydrogen peroxide is added, and compared with embodiment 2, the higher the hydrogen peroxide concentration is, the larger the adhesion between the steel wire and the zinc-aluminum plating layer is, but when the hydrogen peroxide concentration reaches a certain value, the adhesion between the steel wire and the zinc-aluminum plating layer does not change any more.

In the embodiments 12 to 13, the nitrous acid concentration is added, and compared with the embodiment 2, the higher the nitrous acid concentration is, the larger the adhesion between the steel wire and the zinc-aluminum plating layer is.

The embodiments of the present invention are preferred embodiments of the present application, and the scope of protection of the present application is not limited by the embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.