CN113070356A

CN113070356A - Method for removing oxide layer of brass alloy wire rod without pickling

Info

Publication number: CN113070356A
Application number: CN202110257535.7A
Authority: CN
Inventors: 宋卡迪; 宋卡洪; 徐红光; 郎滨
Original assignee: Ningbo Changzhen Copper Co ltd
Current assignee: Ningbo Changzhen Copper Co ltd
Priority date: 2021-03-09
Filing date: 2021-03-09
Publication date: 2021-07-06
Anticipated expiration: 2041-03-09
Also published as: CN113070356B

Abstract

The invention relates to the technical field of copper alloy processing, and provides a method for removing an oxide layer of a brass alloy wire rod without pickling aiming at the problem of high cost of removing the oxide layer on the surface of the wire rod by a pickling-free process. The method for removing the oxide layer is achieved through the assembly line type operation of extension-peeling-extension or extension-peeling-extension, so that the pickling operation process is reduced, the production cost is reduced, and the method is environment-friendly.

Description

Method for removing oxide layer of brass alloy wire rod without pickling

Technical Field

The invention relates to the technical field of copper alloy processing, in particular to a method for removing an oxide layer of a brass alloy wire rod without pickling.

Background

After the brass alloy wire is annealed, a black oxide layer is formed on the surface of the brass alloy wire, and the oxide layer is treated by using a pickling solution in the traditional method. For example, patent CN105369057B discloses a corrosion-resistant and wear-resistant multi-element nickel-brass alloy and a preparation and processing method thereof, the material is obtained by processing treatments such as smelting and casting, primary rolling, primary intermediate annealing, acid washing, intermediate rolling, secondary intermediate annealing, acid washing, finish rolling, low-temperature annealing and the like, and the tensile strength sigma of the copper alloy is the tensile strength_bThe corrosion rate in a simulated seawater test is 0.012-0.015mm/a, the mass abrasion loss is 0.65-0.8mg, and the alloy can be widely applied to copper-based parts such as ship parts, steam and water pipes, but the pickling easily causes environmental pollution and human body damage, and simultaneously the metal surface is easily corroded in the pickling process, and the surface of the brass alloy wire is rough due to the excessive concentration of the acid solution. When the pickling is used, the pickling time and concentration must be controlled, a proper inhibitor is added, and the acid solution is changed irregularly, however, the process is not easy to control, so the problems existing in the prior art can be well solved by the invention without a pickling device and a pickling process.

The pickling-free process can well remove oxide skins and rusty materials on the surfaces of the wires, and meanwhile, the quality of products is remarkably improved. The existing acid-washing-free rust removal technology mainly comprises physical rust removal methods such as a rust removal polishing machine, a shelling rust removal machine, an abrasive belt rust removal machine and the like, but the equipment cost is high, the rust removal effect is not very ideal, and a plurality of defects still exist, such as the abrasive belt rust removal machine, wherein an abrasive belt is used for polishing a product so as to remove oxide skin on the surface. The abrasive belt is an easily-worn part, the service life is short, and particularly in rainy days, the abrasive belt is more easily worn due to the fact that the abrasive belt paper and the wire are wet due to high air humidity. Therefore, the abrasive belt needs to be frequently replaced, and meanwhile, the abrasive belt needs to be adjusted, so that the tension of the abrasive belt meets the requirement, and the working efficiency is greatly reduced. When the abrasive belt machine works, the rust removal is incomplete, and a residual oxide layer is not completely removed, so that the product quality and subsequent processing are influenced. Accordingly, there is a need for an ideal method for removing oxide layers.

Disclosure of Invention

The invention provides a method for removing an oxide layer of a brass alloy wire without pickling, aiming at overcoming the problem that the cost for removing the oxide layer on the surface of the wire can be high due to a pickling-free process.

In order to achieve the purpose, the invention adopts the following technical scheme:

a method for removing an oxide layer of a brass alloy wire rod without pickling comprises the steps of enabling the brass alloy wire rod to pass through an oil groove, then pass through an extension die and a peeling die in a die mounting device, then pass through a wire element of a vertical wire drawing machine, enter an extension die of another die mounting device, and finally pass through an inverted wire drawing machine to obtain a finished product. The wire rod is lubricated through the oil groove and then is extended and peeled, so that the service life of the die can be prolonged, and meanwhile, the fine grain strengthening of the brass alloy wire rod is realized. The method connects the oil groove with the die mounting device, improves the lubricating effect, can produce finished products at one time through the combined device when the equipment works, greatly improves the quality and the precision, removes an oxide layer through peeling instead of acid washing, reduces a production pass and the acid washing process, greatly reduces the production cost, the acid washing cost and the personnel cost, and proves that the daily yield is improved from 4 tons to more than 5 tons through practice, the daily production efficiency is improved by 20-30%, the work efficiency is improved by 35-55%, the die consumption is reduced, and the production speed is accelerated.

Preferably, the number of the peeling molds in the mold mounting device is one or two.

Preferably, the die-attaching device is made of tungsten steel. The die mounting device needs to peel and extend the brass alloy wire, and has high requirement on wear resistance. The tungsten steel (hard alloy) has a series of excellent performances of high hardness, wear resistance, good strength and toughness, heat resistance, corrosion resistance and the like, and has long service life.

Preferably, the peeling process of the peeling die is to pull out 1-3mm of the surface of the brass alloy wire rod. The scalping can replace the acid washing step to remove the oxide layer on the surface of the brass wire.

Preferably, the vertical wire drawing machine adopts a stepless speed change mechanism to adjust the wire take-up speed.

Preferably, the oil groove is filled with lubricating oil, and the components of the lubricating oil comprise: 40-60 parts of Turkey red oil, 10-20 parts of water, 1-3 parts of extreme pressure additive, 3-5 parts of anti-emulsifier, 7-9 parts of finger-sticking agent, 1-3 parts of defoaming agent and 8-10 parts of calcium hydroxide according to parts by weight. Compared with common base oil, the Turkey red oil has better permeability and can quickly permeate to roll away rust and other impurities. The invention needs to carry out peeling treatment on the brass, so the extreme pressure additive is added, and the extreme pressure additive is decomposed under friction and high temperature and can react with metal to generate a compound with lower shearing stress and smelting point than pure metal, thereby preventing the occlusion and bright contact of the contact surface and effectively protecting the metal surface.

As a further preference, the Turkey red oil is subjected to modification treatment, and the treatment step is,

(1) oxidation of Turkey red oil: mixing the Turkey red oil and acetic acid, stirring, heating to 50-60 ℃, dropwise adding a mixed solution consisting of hydrogen peroxide and phosphoric acid, heating to 60-70 ℃ after dropwise adding, and performing alkali washing, water washing and reduced pressure distillation after reaction to obtain epoxidized Turkey red oil;

(2) grafting procyanidin: adding procyanidine and DMC catalyst into ethanol water solution according to a molar ratio of 100 (0.5-1), stirring, heating, dropwise adding epoxidized Turkey red oil until the reaction is finished, keeping the temperature at 70-90 ℃ in the reaction process, removing solvent after the reaction is finished, and vacuum drying to obtain the modified Turkey red oil.

Procyanidin contains a large amount of phenolic hydroxyl groups, is a high-efficiency natural antioxidant, can be extracted from cortex Pini, and has abundant sources. However, the inventor grafts procyanidin into the molecular structure of the turkey red oil through chemical reaction because the turkey red oil has high viscosity and more substances are added into the lubricating oil, procyanidin is not easy to disperse when being directly added into the lubricating oil, and the antioxidant effect is limited. Procyanidin and Taigu oil can not directly react, but the Taigu oil has active functional group of carbon-carbon double bond, so that it is first epoxidized, specifically in H⁺In the presence of hydrogen peroxide, organic acid is pre-oxidized into peroxide organic acid, the peroxide organic acid reacts with unsaturated double bonds in the Turkey red oil to generate epoxidized Turkey red oil, and the epoxidized Turkey red oil is subjected to ring opening and can be connected with hydroxyl of procyanidin to graft procyanidin onto Turkey red oil molecular chains. The modified Turkey red oil has excellent performance, and simultaneously has oxidation resistance, so that the brass alloy after peeling can be prevented from being oxidized; and the procyanidine is a powerful metal chelating agent, can chelate metal ions, and forms an inert compound on the surface of the brass alloy, so that the surface of the brass alloy is further protected.

More preferably, the procyanidin is oligomeric procyanidin of di-pentamer, the mass concentration of the ethanol water solution is 50-70%, and the mass concentration of the procyanidin in the solution is 10-20%.

Preferably, the preparation method of the lubricating oil comprises the following steps: mixing Turkey red oil, water, extreme pressure additive, anti-emulsifier, defoamer and calcium hydroxide according to the parts by weight, heating to 120 ℃ for 100 ℃, stirring for 10-30min, cooling to 50-70 ℃, adding a finger-sticking agent, stirring for 5-10min, and filtering to obtain the lubricating oil.

Therefore, the invention has the following beneficial effects: (1) according to the invention, the scale layer is removed by peeling instead of acid washing, so that a production pass and an acid washing process are reduced, the production cost, the acid washing cost and the personnel cost are greatly reduced, the daily output is improved from 4 tons to more than 5 tons through practice, the daily output efficiency is improved by 20-30%, the work efficiency is improved by 35-55%, the consumption of a die is reduced, and the production speed is accelerated; (2) the oil groove is connected with the die mounting device, so that the lubricating effect is improved, the service life of the die can be prolonged by lubricating the brass alloy wire rod through the oil groove and then extending and peeling the brass alloy wire rod, and meanwhile, the fine grain strengthening of the brass alloy wire rod is realized; (3) the Turkey red oil is modified by procyanidine, so that the lubricating oil has oxidation resistance while maintaining the excellent performance of the lubricating oil, and can prevent the peeled brass alloy from being oxidized; and the procyanidine is a powerful metal chelating agent, can chelate metal ions, and forms an inert compound on the surface of the brass alloy, so that the surface of the brass alloy is further protected.

Drawings

FIG. 1 is a block diagram of an apparatus used in the present invention.

In the figure, 1-oil groove; 2-smoke and dust removing device; 3, a first die mounting device; 4-vertical wire drawing machine; 5, a second die mounting device; 6, an inverted wire drawing machine.

Detailed Description

The technical solution of the present invention is further illustrated by the following specific examples.

In the present invention, unless otherwise specified, all the raw materials and equipment used are commercially available or commonly used in the art, and the methods in the examples are conventional in the art unless otherwise specified.

The structure of the equipment used in the method is shown in figure 1, a first die mounting device 3, a vertical wire drawing machine turntable 4, a second die mounting device 5 and an inverted wire drawing machine turntable 6 are sequentially arranged on a workbench from right to left, wherein an oil groove 1 and a smoke and dust removing device 2 are arranged on the first die mounting device 3, lubricating oil is filled in the oil groove 1, and the smoke and dust removing device 2 is used for absorbing smoke dust, so that the safety and the environmental protection of the production environment are ensured. The vertical wire drawing machine adopts a stepless speed change mechanism to adjust a wire take-up speed die. One or two peeling molds and an extension mold are arranged in the first mounting device 3, and one extension mold is arranged in the second die mounting device 5. The first die mounting device 3 and the second die mounting device 5 are made of tungsten steel.

Example 1

A method for removing an oxide layer of a brass alloy wire rod without pickling comprises the steps of firstly passing the brass alloy wire rod through an oil groove filled with commercially available BPL penetrating lubricating oil, then passing the brass alloy wire rod through an extension die and a peeling die in a die mounting device, wherein the peeling process comprises the steps of pulling out 1-3mm of the surface of the brass alloy wire rod, then passing the brass alloy wire rod through a wire disc of a vertical wire drawing machine, entering the extension die of another die mounting device, and finally passing the brass alloy wire rod through an inverted wire drawing machine to obtain a finished product.

The method connects the oil groove with the die mounting device, improves the lubricating effect, can produce finished products at one time through the combined device when the equipment works, greatly improves the quality and the precision, achieves the method for removing the oxide layer through the streamline type operation of extension-peeling-extension or extension-peeling-extension, reduces the pickling operation process, reduces one production pass and the pickling process, reduces the production cost, the pickling cost and the personnel cost, proves that the daily yield is improved from 4 tons to more than 5 tons through practice, improves the daily yield by 20-30 percent, improves the work efficiency by 35-55 percent, reduces the die consumption and accelerates the production speed.

Example 2

The difference from example 1 is that the lubricating oil is prepared by the following method: according to the mass parts, 50 parts of Turkey red oil, 15 parts of water, 2 parts of extreme pressure additive, 4 parts of anti-emulsifier, 8 parts of finger-sticking agent, 2 parts of defoaming agent and 9 parts of calcium hydroxide are heated to 110 ℃, stirred for 20min, cooled to 60 ℃, added with the finger-sticking agent, stirred for 8min and filtered to obtain the lubricating oil.

Example 3

The difference from the example 2 is that the Turkey red oil in the example is modified by the following steps,

(1) oxidation of Turkey red oil: adding 50g of Turkey red oil and 1g of acetic acid into a flask, stirring and heating to 40 ℃, dropwise adding a mixed solution consisting of 3.6g of 30% hydrogen peroxide and 0.8g of phosphoric acid, heating to 60 ℃ after dropwise adding, carrying out alkali washing and water washing to neutrality after reaction, and carrying out reduced pressure distillation under 0.08MPa to obtain epoxidized Turkey red oil;

(2) grafting procyanidin: adding trimeric oligomeric procyanidin and DMC catalyst into 60 wt% ethanol water solution according to the molar ratio of 100:0.6, wherein the mass concentration of procyanidin in the solution is 15%, dropwise adding epoxidized Turkey red oil under stirring and heating conditions until the reaction is finished, keeping the temperature at 80 ℃ in the reaction process, removing the solvent after the reaction is finished, and performing vacuum drying to obtain the modified Turkey red oil.

Comparative example 1

The difference from example 1 is that the lubricating oil, in this comparative example, was prepared by the following method: according to the mass parts, 50 parts of Turkey red oil, 15 parts of water, 2 parts of extreme pressure additive, 4 parts of anti-emulsifier, 8 parts of finger-sticking agent, 2 parts of defoaming agent, 9 parts of calcium hydroxide and 2 parts of oligomeric procyanidin trimer are heated to 110 ℃, stirred for 20min, cooled to 60 ℃, added with the finger-sticking agent, stirred for 8min and filtered to obtain the lubricating oil.

Performance testing

In order to verify that the modified lubricating oil has excellent oxidation resistance, brass products in the same shape and quality in each example and comparative example are cut out, and are subjected to oxidation heating for 2 hours at the temperature of 700 ℃, and the oxidation resistance of the modified lubricating oil is evaluated by adopting a weight gain method. The results show that the weights of examples 1-3 are respectively increased by 0.021g, 0.020g and 0.011g, and the increase of 0.015g in comparative example 1 indicates that the oxidation resistance of the modified Turkey red oil can be remarkably improved when the modified Turkey red oil is used for treating brass alloy wires by utilizing the procyanidine, and the oxidation resistance is better when the modified Turkey red oil is directly added with the procyanidine compared with the comparative example 1.

Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

1. The method for removing the oxide layer of the brass alloy wire rod without pickling is characterized in that the brass alloy wire rod firstly passes through an oil groove, then passes through an extension die and a peeling die in a die mounting device, then passes through a disc element of a vertical wire drawing machine, enters an extension die of another die mounting device, and finally passes through an inverted wire drawing machine to obtain a finished product.

2. The method for removing the oxide layer from the brass alloy wire rod without pickling according to claim 1, wherein the number of the peeling die in the die mounting device is one or two.

3. A method of pickling-free removal of an oxide layer from a brass alloy wire as recited in claim 1 or 2 in which said die attachment means is made of tungsten steel.

4. The method for removing the oxide layer of the brass alloy wire rod without pickling according to claim 1, wherein the peeling process of the peeling die is to pull out 1-3mm of the surface of the brass alloy wire rod.

5. The method for removing the oxide layer from the brass alloy wire rod without acid washing according to claim 1, wherein the vertical wire drawing machine adopts a stepless speed change mechanism to adjust the wire take-up speed.

6. A method of pickling-free removal of an oxide layer from a brass alloy wire as recited in claim 1 in which said oil bath contains a lubricating oil having a composition comprising: 40-60 parts of Turkey red oil, 10-20 parts of water, 1-3 parts of extreme pressure additive, 3-5 parts of anti-emulsifier, 7-9 parts of finger-sticking agent, 1-3 parts of defoaming agent and 8-10 parts of calcium hydroxide according to parts by weight.

7. The method for removing the oxide layer from the brass alloy wire rod without pickling according to claim 6, wherein the Turkey red oil is modified by the steps of,

8. The method for removing the oxide layer of the brass alloy wire rod without pickling as claimed in claim 7, wherein the procyanidin is a di-pentamer oligomeric procyanidin, the mass concentration of the ethanol water solution is 50-70%, and the mass concentration of the procyanidin in the solution is 10-20%.

9. A method for removing an oxide layer from a brass alloy wire without pickling according to any of claims 6 to 8, wherein said lubricating oil is prepared by: mixing Turkey red oil, water, extreme pressure additive, anti-emulsifier, defoamer and calcium hydroxide according to the parts by weight, heating to 120 ℃ for 100 ℃, stirring for 10-30min, cooling to 50-70 ℃, adding a finger-sticking agent, stirring for 5-10min, and filtering to obtain the lubricating oil.