CN100376711C - A kind of thermal spraying zinc-aluminum alloy wire rod and preparation method thereof - Google Patents

Abstract

The present invention relates to a hot spraying alloy wire, more specifically to a hot spraying Zn-Al alloy wire ingredient and a preparation method thereof. The hot spraying alloy wire is prepared from 10 wt% to 20 wt% of Al, M, less than 1% of the total amount of impurities, and the balance of Zn, wherein M is smaller than or equal to 1.5 wt% and larger than or equal to 0.006 wt%; M is RE or Mg or Ti or B or the combination thereof. The preparation method of the hot spraying alloy wire comprises the steps that firstly, a Zn ingot and an Al ingot are added to an alloy smelting furnace to be heated and smelted; intermediate alloy is added after refinement to be agitated until the intermediate alloy is completely smelted; horizontal continuous casting is carried out after static placement and slag removal; a Zn-Al alloy rough blank thick line obtained by horizontal and continuous casting is processed in a homogenizing anneal mode, the rough blank thick line is drawn and contracted to form a Zn-Al alloy wire product. The present invention has the advantages that basal steel is sufficiently protected, and the service life of the basal steel is extended.

Description

A kind of thermal spraying zinc-aluminum alloy wire rod and preparation method thereof

technical field

The invention relates to a thermal spraying alloy wire, in particular to a thermal spraying zinc-aluminum alloy wire composition and a preparation method thereof.

Background technique

The thermal spraying process is used to spray zinc, aluminum or its alloy wires on the surface of steel components to form a metal coating, which can protect steel facilities in various corrosive environments for a long time. Thermal sprayed zinc and thermal sprayed aluminum coatings have their own advantages. Thermal sprayed zinc coating has a good cathodic protection effect on steel, while thermal sprayed aluminum coating has superior corrosion resistance and impact resistance. If it is combined, spraying zinc-aluminum alloy on the steel can not only provide good cathodic protection performance, but also have corrosion resistance, prolonging the life of the steel. Therefore, zinc-aluminum alloy wire is trusted by people, but the commonly used zinc-15% aluminum alloy wire also has its own weakness, that is, it is prone to intergranular corrosion. Adding alloying elements such as rare earth, titanium, and magnesium to zinc-aluminum alloys can refine the grains of zinc-aluminum alloys and improve plasticity and corrosion resistance. It should be a good way to avoid intergranular corrosion, but at present There are no reports of successful cases.

The horizontal continuous casting technology of metal materials is a high-tech technology used to produce high-alloy wire rods that are difficult to deform. However, there is no relevant report on the production of zinc-aluminum alloy wire rods in the field of thermal spraying.

Contents of the invention

The purpose of the present invention is to provide a thermal sprayed zinc-aluminum alloy wire rod with excellent corrosion resistance, so that the base steel can be fully protected and prolong its service life; at the same time, the purpose of the present invention is also to develop a thermal sprayed zinc-aluminum alloy wire rod. The horizontal continuous casting method can be used for directly forming zinc-aluminum alloy wire rods.

The present invention is characterized in that: by weight percentage, the composition of thermal sprayed zinc-aluminum alloy wire components is: Al: 10% to 20%; 0.006%≤M≤1.5%; the total amount of impurities (Fe , Si, etc.); the balance is Zn; wherein M is one of RE (RE refers to mixed rare earth metals containing cerium mass fraction ≥ 45%, wherein the total mass fraction of rare earth metals ≥ 98%), Mg, Ti or B , two, three or four combinations; details are as follows:

1) If it is one of the components, it is respectively: RE is 0.015% to 0.5% of the total amount, or Mg is 0.03% to 0.5% of the total amount, or Ti is 0.03% to 0.5% of the total amount, or B is 0.006% to 0.1% of the total amount;

2) If it is two of them, it is RE and Mg (or Ti) accounting for 0.06% to 0.5% of the total amount and 0.03% to 0.5% of the total amount respectively, and the ingredients RE, Mg or Ti should satisfy RE: Mg (or Ti) = 1: (0.5 ~ 8); or 0.03% ~ 0.5% of the total amount of Mg and 0.03% ~ 0.5% of the total amount of Ti, wherein the ingredients Ti and Mg should satisfy Ti: Mg = 1 : (0.5～2); or be 0.03%～0.5% of Ti and B of 0.003%～0.05% of the total amount, wherein the ingredients Ti and B should satisfy Ti:B=(3～10):1;

3) If there are three components, they are respectively 0.015% to 0.5% of the total amount of RE and 0.03% to 0.5% of the total amount of Ti, and 0.03% to 0.5% of the total amount of Mg (or 0.003% of the total amount) %～0.05% of B), wherein RE, Ti, Mg or B should satisfy RE:Ti:Mg=1:(0.5～2.5):(0.5～2.5), or RE:Ti:B=(5～25) : (5～10): 1; or Mg accounting for 0.03%～0.5% of the total amount, Ti accounting for 0.03%～0.5% of the total amount, and B accounting for 0.003%～0.05% of the total amount, wherein Mg, Ti and B should satisfy Mg:Ti:B=(5~20):(5~10):1;

4) If there are four components, they are RE accounting for 0.015%-0.5% of the total amount, Mg accounting for 0.03%-0.45% of the total amount, Ti accounting for 0.03%-0.5% of the total amount, and 0.003% of the total amount ~0.05% B should satisfy RE:Mg:Ti:B=(5~50):(2.5~10):(5~10):1.

Its concrete preparation method is:

1) First add zinc ingots and aluminum ingots of the required quality into the alloy melting furnace to heat and melt them. When the melting temperature is higher than or equal to 923K, refine them, then add the intermediate alloys of the required quality, and stir until the melting is clear and static. Set aside for 0.5 to 2 hours, remove slag and transfer to heat preservation crystallization furnace for horizontal continuous casting;

2) Adjust the furnace temperature of the thermal insulation crystallization furnace to ensure that the temperature of the alloy liquid in the furnace is stable at the melting point of 60-220K, so as to avoid overheating that affects the formation of the solid shell and the heat of the core of the wire billet returns to the surface to cause surface defects; the alloy liquid in the furnace The height of the surface is kept within the range of 3-20mm higher than the discharge hole on the crystallizer to maintain the needs of multi-line continuous production and balanced hydraulic pressure to push the wire crystallized from the discharge hole to extend outward; the alloy liquid passes through the water cooling system The cooling is gradually solidified to form a cast wire, and is drawn into the wire groove by the traction device at a certain linear speed, and the drawn wire blank enters the coiling device through the wire groove to be wound into a circle; the crystallizer can use an asbestos cement board mold or Copper crystallizer, pull-casting alloy wire billet pulling speed is usually controlled at 0.010-0.020m/s; cooling temperature of asbestos cement board mold is between 288-328K, cooling water position is 5-50 mm away from die hole, water pressure The degree is to not break through the skin of the wire billet just out of the die hole, and keep the water pressure stable; when using a copper crystallizer to produce alloy wire wool, the water pressure should be kept at 0.12～0.15×10 ⁵ Pa; Cooling water needs to be passed in. When the casting speed is 0.010-0.015m/s, the outlet water temperature should be kept between 313-318K, and when the casting speed is 0.015-0.020m/s, it should be between 308-313K ;

3) The zinc-aluminum alloy rough wire obtained by horizontal continuous casting is homogenized and annealed at 473-573K for 1.5-3.0 hours, and then drawn and reduced for 3-8 times to form a zinc-aluminum alloy wire product, and Coiled into a circle.

The present invention has the following advantages:

1. The invention solves the problems of difficult forming of zinc-aluminum alloy, low yield, short wire length, and inconvenient construction, and the equipment is simple, easy to operate, and can cast many strands of wool at the same time, so it is suitable for large and medium-sized factories. Mass production.

2. The surface quality of the zinc-aluminum alloy casting wire of the horizontal continuous casting of the present invention is good, bright and free of scratches. At the same time, due to the high cooling intensity, the precision of the casting wire is improved, the ellipticity is reduced, and the casting wire is increased. Density, obtained near-final shaped wire blanks, which can be subjected to simple heat treatment and secondary cold processing such as wire drawing and diameter reduction, to obtain finished wires that meet the needs of thermal spraying construction.

3. The zinc-aluminum alloy wire rod prepared by the present invention has excellent corrosion resistance and mechanical properties, and can be used as a new type of thermal spraying material suitable for on-site construction, so that it can be used in industrial atmosphere areas, marine atmosphere areas, spray splash areas, tidal range areas and Large steel structures used in corrosive environments such as full immersion areas can be fully protected and their service life extended.

Description of drawings

Fig. 1 is a schematic structural diagram of the horizontal continuous casting equipment for zinc-aluminum alloy wire blanks of the present invention.

Detailed ways

The present invention will be described in detail below in conjunction with specific embodiments.

Example 1

The weight percentages of the main elements of the wire rod are shown in Table 1.

Table 1 Example 1 wire composition example (wt%)

Al Mg Ti B Fe+Si+Cu Zn 15% 0.50% 0.50% 0.05% ≤1.00% Surplus

preparation:

The structural schematic diagram of the horizontal continuous casting equipment adopted in the present invention is shown in Fig. 1 . Among them: 1 is heat preservation crystallization furnace; 2 is crystallizer; 3 is pressing roll; 4 is pulling roll; 5 is coiling device; 6 is cooling water pipe;

1) Preheat the crucible of the smelting furnace to dark red, add zinc ingots with a mass fraction of 90%, then add aluminum ingots, heat and melt, and when the temperature of the melt reaches 923K or more, use a refining agent with a mass fraction of 0.1 to 0.3% ( This embodiment adopts 0.2% zinc chloride) to refine, add the remaining zinc ingots, and use a graphite bell jar to melt the preheated aluminum-magnesium and aluminum-titanium-boron master alloys with a particle size of 10 to 20 mm (in order to prevent oxidation, the master alloys are made of aluminum foil) package) and press in, stirring constantly, until melted. After standing still for 0.5 hours, remove the slag and transfer to the heat preservation crystallization furnace, and then carry out horizontal continuous casting after adjusting the temperature.

2) Adjust the furnace temperature of the thermal insulation crystallization furnace to ensure that the temperature of the alloy liquid in the furnace is stable at 180K higher than the melting point, so as to avoid overheating that affects the formation of the solid shell and the heat of the core of the wire billet returns to the surface to cause surface defects; the alloy liquid in the furnace The height of the surface is kept within the range of 3-20mm higher than the discharge hole on the crystallizer to maintain the needs of multi-line continuous production and balanced hydraulic pressure, and push the wire crystallized from the discharge hole to extend outward. The mold 2, the traction device composed of the pressure roller 3, the wire groove 7, the pulling roller 4 and the coiling device 5 are arranged in a horizontal line, and the alloy liquid is gradually solidified through the cooling of the water cooling system to form a cast wire, and the casting wire is formed at a certain line speed The traction device is introduced into the wire groove 7. When the condensation and crystallization speed of the alloy liquid is balanced with the pulling speed, the zinc-aluminum alloy wire rod is continuously cast from the horizontal direction. The wire blank drawn out enters the coiling device 5 through the wire groove and is wound into a circle. The crystallizer adopts asbestos cement plate mold, and the pulling speed of the drawing-casting alloy wire billet in this embodiment is controlled at 0.010m/s. The cooling temperature of the asbestos cement board mold is 298K, the cooling water position is 50 mm away from the mold hole, and the water pressure should not break through the skin of the wire blank just out of the mold hole, and keep the water pressure stable. The zinc-aluminum alloy is horizontally continuous casted to obtain rough rough wires of φ4.2-4.5mm.

3) The thick zinc-aluminum alloy rough wire obtained by horizontal continuous casting is subjected to homogenization annealing at 473K, and air-cooled after holding for 2 hours. After uniform annealing, the blank is drawn and reduced in 4 passes to obtain zinc-aluminum alloy wire of φ3.00 _-0.10 ^+0.00 mm, and coiled into a circle. The length of a single alloy wire is ≥15m, and the product bundle weight is 25.0± 1.0kg.

The zinc content in the zinc-aluminum alloy involved in the present invention is relatively high, and its plasticity and deformability are relatively difficult, which undoubtedly increases the production cost of the conventional forging and rolling process. However, the present invention adopts the horizontal continuous casting method for High-tech technologies for the production of hard-to-deform high-alloy wires have greatly improved this situation.

Example 2

The difference from Example 1 is that: the composition of the wire rod is: Al, 20%; RE, 0.5%; impurity, less than 1%; the balance is Zn. Copper crystallizers are used to cast alloy wire wool. The alloy liquid temperature in the furnace is stable at 60K higher than the melting point, the casting speed is 0.015m/s, the cooling water pressure is 0.15×10 ⁵ Pa, and the outlet water temperature is 308K. The rough rough wire is homogenized and annealed at 513K for 3.0 hours, and then drawn and reduced 8 times to form a zinc-aluminum alloy wire product of φ2.00 _-0.10 ^+0.00 mm, and coiled into a coil.

Example 3

The difference from Example 1 is that: the composition of the wire rod is: Al, 10%; RE, 0.06%; Mg, 0.03%; impurity, less than 1%; the balance is Zn. Copper crystallizers are used to cast alloy wire wool. The alloy liquid temperature in the furnace is stable at 80K higher than the melting point, the casting speed is 0.015m/s, the cooling water pressure is 0.12×10 ⁵ Pa, and the outlet water temperature is 308K. The rough rough wire was subjected to a homogenization annealing treatment at 493K for 3.0 hours.

Example 4

The difference from Example 1 is that the wire rod composition is: Al, 15%; RE, 0.06%; Mg, 0.03%; Ti, 0.03%; B, 0.003%; impurity, less than 1%; the balance Zn. The casting speed is 0.015m/s, the cooling water pressure is 0.15×10 ⁵ Pa, and the outlet water temperature is 318K. The rough rough wire was subjected to a homogenization annealing treatment at 513K for 2.0 hours.

Claims (9)

1. thermospray Zinc-aluminum alloy wire, it is characterized in that: by weight percentage, its component is: Al:10%～20%; 0.006%≤M≤1.5%; Total amount less than, equal 1% impurity; Surplus is Zn; Wherein M is Mg, RE+Mg, RE+Ti, Mg+Ti, RE+Ti+Mg, RE+Ti+B, Mg+Ti+B or RE+Ti+Mg+B.

2. according to the described thermospray Zinc-aluminum alloy wire of claim 1, it is characterized in that: when described M is Mg, be 0.03%～0.5% of total amount.

3. according to the described thermospray Zinc-aluminum alloy wire of claim 1, it is characterized in that: when described M is RE+Mg or RE+Ti, for: account for the RE of total amount 0.06%～0.5% and account for the Mg or the Ti of total amount 0.03%～0.5%, composition RE wherein, Mg or Ti should satisfy RE: Mg or Ti=1: (0.5～8); When M is Mg+Ti, be Mg that accounts for total amount 0.03%～0.5% and the Ti that accounts for total amount 0.03%～0.5%, wherein composition Ti and Mg should satisfy Ti: Mg=1: 0.5～2.

4. according to the described thermospray Zinc-aluminum alloy wire of claim 1, it is characterized in that: when described M is RE+Ti+Mg or RE+Ti+B, for: the RE and the Ti that accounts for total amount 0.03%～0.5% that account for total amount 0.015%～0.5%, and account for the Mg of total amount 0.03%～0.5% or account for the B of total amount 0.003%～0.05%, RE wherein, Ti, Mg or B should satisfy RE: Ti: Mg=1: 0.5～2.5: 0.5～2.5, or RE: Ti: B=5～25: 5～10: 1; When M is Mg+Ti+B,, account for the Ti of total amount 0.03%～0.5% for accounting for the Mg of total amount 0.03%～0.5%, and the B that accounts for total amount 0.003%～0.05%, satisfy Mg: Ti: B=5～20: 5～10: 1.

5. according to the described thermospray Zinc-aluminum alloy wire of claim 1, it is characterized in that: when described M is RE+Ti+Mg+B, for: the RE that accounts for total amount 0.015%～0.5%, account for the Mg of total amount 0.03%～0.45%, account for the Ti of total amount 0.03%～0.5%, and the B that accounts for total amount 0.003%～0.05%, should satisfy RE: Mg: Ti: B=5～50: 2.5～10: 5～10: 1.

6. the preparation method of a thermospray Zinc-aluminum alloy wire is characterized in that:

1) elder generation adds heat fused in the alloy melting stove with zinc ingot metal, the aluminium ingot of required quality, when smelting temperature is higher than, carries out refining after equaling 923K, the master alloy that adds required quality then, be stirred to molten clear, leave standstill 0.5～2 hour, be transferred to the insulation crystal growing furnace after skimming and prepare to carry out horizontal continuous-casting;

2) horizontal casting: adjust insulation crystal growing furnace furnace temperature, guarantee that the alloy liquid temp in the stove is stabilized in fusing point 60～220K; Alloy liquid level in the stove remains in the scope that is higher than crystallizer top discharge hole 3～20mm, alloy liquid is solidified gradually by the cooling of water-cooling system, form the casting silk, and be pulled device lead-in conductor groove by certain linear velocity, the wire rod blank of pulling out enters the lopping of take-up mechanism coiling through metallic channel;

3) the aluminium zinc blank thick line of horizontal casting acquisition, the homogenizing annealing that carried out under 473～573K 1.5～3.0 hours is handled, and becomes the Zn-Al alloy wire product again and through 3～8 drawings, tube reducings, and the coiling lopping.

7. according to the preparation method of the described thermospray Zinc-aluminum alloy wire of claim 6, it is characterized in that: the pulling speed of described cast alloy wire base is controlled at 0.010～0.020m/s usually.

8. according to the preparation method of the described thermospray Zinc-aluminum alloy wire of claim 6, it is characterized in that: described crystallizer can adopt the asbestos cement plate mould, its cooling temperature is between 288～328K, the water coolant position is apart from 5～50 millimeters of nibs, hydraulic pressure to be breaking through the line base epidermis degree of being that just goes out nib, and keeps stable water pressure.

9. according to the preparation method of the described thermospray Zinc-aluminum alloy wire of claim 6, it is characterized in that: described crystallizer can adopt copper crystallizer, and its cooling water pressure should remain on 0.12～0.15 * 10 ⁵Pa, when casting speed was 0.010～0.015m/s, leaving water temperature(LWT) remained between 313～318K, and when casting speed was 0.015～0.020m/s, leaving water temperature(LWT) should remain between 308～313K.