CN114211049A

CN114211049A - Tungsten wire alloy wire, diamond wire saw made of tungsten wire alloy wire, and preparation method and application of tungsten wire alloy wire

Info

Publication number: CN114211049A
Application number: CN202210015300.1A
Authority: CN
Inventors: 张福军; 李信; 韩登峰
Original assignee: Jiangsu Jucheng Diamond Technology Co ltd
Current assignee: Jiangsu Jucheng Diamond Technology Co ltd
Priority date: 2022-01-07
Filing date: 2022-01-07
Publication date: 2022-03-22

Abstract

The preparation method comprises the following steps: (1) preparing an alloy tungsten wire bus, namely preparing a raw material → reducing → doping → reducing → isostatic pressing → sintering → vertical melting → rotary swaging → annealing → drawing → electrolyzing to prepare a 30-50 mu m silvery white metallic luster alloy tungsten wire; (2) and (2) sequentially carrying out paying-off → pretreatment → impact plating → sanding → sand consolidation → post-treatment → take-up on the alloy tungsten wire obtained in the step (1) to prepare the alloy tungsten wire diamond fretsaw. (3) And (3) matching the alloy tungsten wire diamond wire saw prepared in the step (2) with a customer cutting technology for use, wherein the cutting technology mainly comprises guide wheel parameter optimization, cutting fluid PH adjustment, cutting tension and the like. The alloy tungsten wire bus provided by the invention has the advantages of thinner specification, higher strength, low brittle failure frequency, good conductivity, corrosion resistance and the like, greatly reduces the wire breakage rate of a production process and a client application end, and can realize the advantages of low wire breakage during cutting, high cutting efficiency and good silicon wafer quality.

Description

Tungsten wire alloy wire, diamond wire saw made of tungsten wire alloy wire, and preparation method and application of tungsten wire alloy wire

Technical Field

The invention belongs to the field of wire saw cutting, and particularly relates to a tungsten wire alloy wire, a diamond wire saw made of the tungsten wire alloy wire, and a preparation method and application of the tungsten wire alloy wire.

Background

The diamond wire saw is characterized in that diamonds are fixedly connected on the surface of a bus, the cutting efficiency is high, the cutting quality is excellent, and the like, and the diamond wire saw is widely applied to wire cutting industries of photovoltaic silicon wafers, semiconductors, sapphires, magnetic materials and the like.

In the application field of the diamond wire, the manufacturing cost of the tungsten bus is 2-3 times of that of carbon steel with the same specification, so that the market popularization is hindered due to high cost; the preparation literature of the singly doped Re or La alloy tungsten wire is reported, but the improvement of the strength or the toughness and the like is not obvious, so that the industrialization in the field of silicon wafer cutting is not reported.

Meanwhile, with the development of the photovoltaic silicon wafer diamond wire saw industry, the silicon wafer cutting is developed to be thin and large so as to meet the requirements of more wafers produced by customers, good silicon wafer quality, high efficiency and the like. Therefore, the requirements of the diamond wire saw on thinner diameter, higher strength, better toughness, more uniform diamond, lower broken wire and the like are provided. At present, 92 carbon or 100 carbon raw materials are basically adopted in the field of mass-produced diamond wire saws as carriers, but due to the fact that the diameter is thin, the carbon steel raw materials cannot meet the industrial requirements due to the defects of inclusion, non-fine grains, insufficient strength and the like, and the finding of other material buses has great significance for cutting of the diamond wire saws.

Disclosure of Invention

In order to overcome the defects in the prior art, the invention aims to provide a tungsten wire alloy wire, a diamond wire saw made of the tungsten wire alloy wire, a preparation method and application of the diamond wire saw, and the specific technical scheme is as follows:

a tungsten wire is doped with 0.03-20% of Re and/or 0.01-15% of La by weight, the diameter of the tungsten wire is 30-50 mu m, the strength is not less than 5100Mpa, and the elastic modulus is 350-450 Gpa.

Preferably, the tungsten wire is doped with 3-20% of Re or/and 2.5-15% of La in percentage by weight;

a method of making a tungsten wire alloy wire comprising the steps of:

step 1: reducing raw material tungsten powder by hydrogen, and then carrying out acid pickling and impurity removal to obtain tungsten powder with the purity of more than or equal to 99%;

step 2: spraying a rhenium nitrate solution and a lanthanum nitrate solution on the tungsten powder obtained in the step (1), and stirring and mixing to ensure that the doping amount Re is 0.03-20 wt% or/and La is 0.01-15 wt%;

and step 3: performing primary hydrogen reduction on the mixed tungsten powder obtained in the step 2 in a 700 ℃ hydrogen reduction furnace, and performing secondary hydrogen reduction in a 850 ℃ hydrogen reduction furnace to obtain mixed alloy tungsten powder, wherein preferably, the concentration of hydrogen used in the two-time reduction is not lower than 99%;

and 4, step 4: performing isostatic pressing molding on the mixed alloy tungsten powder obtained in the step 3 to obtain the mixed alloy tungsten powder with the density of 8.0-15 g/cm³A semi-finished product with molding strength;

and 5: pre-sintering the semi-finished product obtained in the step 4 at the sintering temperature of 1200 ℃ for 45-65 min, and then performing vertical melting sintering at the sintering temperature of 2900 ℃ for 110-130 min;

step 6: performing rotary forging cogging on the product obtained in the step 5, and then performing annealing treatment in a hydrogen protection heating furnace, wherein the annealing temperature is 1100 ℃;

and 7: and (4) continuously and rotatably forging the product obtained in the step (6) to prepare an alloy tungsten rod with the diameter of 2-3mm, uniformly coating the surface of the alloy tungsten rod with graphite emulsion, and drawing the alloy tungsten rod to a tungsten wire alloy wire with the diameter of 30-50 microns through a diamond die. Preferably, the tungsten wire alloy wire is drawn to a diameter of 30-50 mu m through a 36-pass diamond die.

Further, the acid washing and impurity removal in the step 1 adopt a mixed solution of sulfamic acid and hydrochloric acid, wherein the concentration of sulfamic acid is 50g/L, and the concentration of hydrochloric acid is 60ml/L, so as to improve the adsorption uniformity of the tungsten powder on the doping elements.

Preferably, the doping amount in the step 2 is 3-20 wt% of Re or/and 2.5-15 wt% of La.

Preferably, the parameters of isostatic pressing in the step 3 are 150-230 MPa, and the isostatic pressing is kept for 30-60 min.

Furthermore, the diamond mold in the step 7 adopts a 7.5-degree small-angle diamond mold, and aims to reduce the compression ratio of the steel wire, improve the stress residue of the steel wire and make the deformation of the tissue more uniform; the graphite emulsion adopts D50 0.2um nanometer graphite powder, can make lubricating property more even, reduces the damage to the mould and avoids drawing the production of slot defect.

A diamond wire saw prepared from the tungsten wire alloy wire sequentially comprises a tungsten wire alloy bus, a pre-plated nickel layer, a sand nickel coating layer and a sand fixing nickel layer from inside to outside, wherein the diameter of the diamond wire saw is 45-65 mu m, the breaking tension is 6.5-11N, the diamond wire saw has excellent flexibility, and the bending brittle failure frequency is 0/10 times; the corrosion resistance is better, and the salt spray resistance test is 72h and 10 grades; the diamond wire saw with high cutting force can realize the single wire consumption of 0.9-2.2 m/silicon wafer. The thickness of the nickel pre-plating layer is 30-500 nm, the covering capacity of the nickel pre-plating layer is improved, the magnetism required by sanding is met, and the sanding capacity of the alloy tungsten wire bus in the electroplating process is effectively improved.

A method for preparing the diamond wire saw comprises the following steps:

step 1: paying off a tungsten wire, and treating for 6s by using a NaOH alkali liquor station with the concentration of 60 g/L; then treating for 3.5s by using an amino sulfonic acid station with the concentration of 50 g/L;

step 2: impact plating, wherein the impact plating is nickel sulfamate electroplating, the Ni content is 90g/L, the boric acid content is 35g/L, the nickel chloride content is 8g/L, the current density is 7ASD, and the thickness of an impact plating layer is 100 nm;

and step 3: sanding, wherein sanding is nickel sulfamate electroplating, Ni is 100g/L, boric acid is 30g/L, nickel chloride is 6g/L, current density is 9ASD, the particle size of diamond D50 in the sanding electroplating solution is 7.2 mu m, and the concentration of diamond is 2.0 g/L;

and 4, step 4: consolidation, namely nickel sulfamate electroplating, wherein the Ni is 110g/L, the boric acid is 35g/L, the nickel chloride is 8g/L, and the current density is 9.5 ASD;

and 5: and (3) post-treatment, wherein the post-treatment comprises washing with pure water at normal temperature, drying at 180 ℃, and taking up and winding to obtain the diamond wire saw with the wire diameter of 45-65 mu m.

Furthermore, graphite emulsion exists on the surface of the doped alloy tungsten wire, and the graphite emulsion can affect the binding force of the coating, an electrolysis mode is adopted in the step 1, the metal on the surface is dissolved by using a steel wire as an anode, so that the graphite attached to the surface is removed without a carrier, a fresh base material is exposed, the bonding force between nickel and tungsten atoms is improved, and the binding force between the coating and the alloy tungsten wire is improved.

A method for using a diamond wire saw comprises the steps of rewinding a tungsten wire alloy wire saw to a grooving guide wheel under the tension of 3.5-6.0N to form a running densely-distributed wire net with the speed of 600-2100 m/min, pressing a silicon rod to be cut into the densely-distributed wire net under the cooling of cutting liquid at the table speed of 200-2100 mm/min, and cutting the silicon rod into silicon wafers with the same thickness by using the diamond cutting force of the tungsten wire alloy wire saw; the length of the wire mesh is 4.5-8.0 km, the diameter of the slotted guide wheel is 190-210 mm, the included angle of the slot is 20-40 degrees, the slot depth of the guide wheel is 150-240 mu m, and the R angle of the slot of the guide wheel is 20-45 degrees; the cutting liquid is a high-COD (high molecular organic matter such as a surfactant, a corrosion inhibitor, a dispersant, a builder and the like) cutting aqueous solution, the PH value of the cutting aqueous solution is controlled to be 3.5-6.5, the cutting process table speed interval is 200-2100 mm/min, and the linear speed interval is 600-2100 m/min.

Preferably, the grooved guide wheel is two-axis or three-axis.

According to the invention, by combining a metal structure with a dispersion strengthening and solid solution strengthening mechanism and doping Re and La rare earth elements, the size of metal precipitated crystal grains is reduced, the structure is more compact, the strength and plasticity of the tungsten wire are comprehensively improved, and the tungsten wire has high tensile strength and flexibility under a small diameter. The graphite emulsion exists on the surface of the doped alloy tungsten wire, the graphite emulsion has the binding force due to the shadow coating, an electrolysis mode is adopted in the production, the steel wire is used as an anode to dissolve metal on the surface, so that the graphite attached to the surface is separated by losing the carrier, a fresh base material is exposed, the bonding force between nickel and tungsten atoms is improved, and the binding force between the coating and the alloy tungsten wire is improved.

According to the invention, alloy tungsten wires are used as carriers, Re and La elements are doped to realize the performances of high strength, corrosion resistance, low brittle failure frequency and the like, meanwhile, the impact plating thickness is optimized in the production process of the diamond wire saw to achieve the effect of improving the sanding capacity, and the cutting process with the guide wheel parameters, low cutting liquid PH and high cutting tension is developed, so that the requirements of thin wire, low wire breakage rate, good silicon wafer quality, high efficiency and the like of customers are met, and the requirements of lower single cutter wire consumption, higher cutting efficiency, lower TTV average value and lower short wire rate of the customers are met. The cutting tool can be applied to wire cutting industries of photovoltaic silicon wafers, semiconductors, sapphires, magnetic materials and the like.

Drawings

FIG. 1 is a flow chart of a manufacturing process of a diamond wire saw made of a tungsten wire alloy wire according to the present invention;

FIG. 2 is a schematic view of a diamond wire saw pre-plated with nickel layer;

FIG. 3 is a schematic diagram of guide wheel parameters in the alloy tungsten wire diamond wire saw cutting technology of the invention.

Detailed Description

The method of the present invention is illustrated by the examples, which are to be understood as merely illustrative and not restrictive of the scope of the invention. It should be understood that various changes and modifications can be made by those skilled in the art after reading the disclosure of the present invention, and equivalents fall within the scope of the appended claims.

The starting materials used in the following examples are all commercially available.

Comparative example

The utility model provides a superfine high strength alloy tungsten filament diamond wire saw, comprises alloy tungsten filament generating line and surperficial nickel layer metal consolidation diamond, the generating line is doping Al, As, Ga element alloy tungsten filament, the nickel plating is the nickel sulfamic acid system, diamond D50 particle size is 7.2 mu m.

Preparing an alloy tungsten wire bus:

1. after primary hydrogen reduction, the tungsten powder is doped with Al, As and Ga oxides and stirred and mixed, and the mass ratio of the mixture added is 7:65:1, and the mass of the mixture accounts for 0.1-0.3% of the total mass ratio.

2. And (3) reducing the tungsten powder doped in the step (1) in a hydrogen reduction furnace at 700 ℃, carrying out secondary reduction in a hydrogen reduction furnace at 850 ℃, and carrying out acid pickling and material mixing to obtain the mixed alloy tungsten powder.

3. And (3) performing isostatic pressing molding on the mixed powder obtained in the step (2) to obtain a semi-finished product with certain density and strength.

4. And (3) pre-sintering the semi-finished product in the step (3), wherein the sintering temperature is 1200 ℃, and then performing vertical melting sintering, wherein the sintering temperature is 2900 ℃.

5. And (4) performing rotary swaging and cogging on the sample in the step (4), and then performing annealing treatment in a hydrogen protection heating furnace, wherein the annealing temperature is 1100 ℃.

6. And (5) continuously carrying out rotary swaging on the sample obtained in the step (5) to obtain the required diameter, and carrying out wire drawing, wherein the wire drawing die is a diamond die, the wire drawing lubricating liquid is graphite emulsion, and the black wire with the graphite emulsion attached to the surface is prepared, and the diameter of the black wire is 44 microns.

7. And (3) subjecting the 44-micron tungsten wire alloy sample obtained in the step (6) to electrolytic treatment, wherein the electrolyte is NAOH and the concentration is 100g/L, so as to prepare a 43-micron white alloy tungsten wire, the diameter of the tungsten wire is 43 +/-0.5 micron, the breaking force is not less than 7.3N, and the elastic modulus is 332 Gpa.

Preparing an alloy tungsten wire diamond wire:

(1) paying off the alloy tungsten wire bus, performing pretreatment, and cleaning the surface of the alloy tungsten wire bus, wherein the pretreatment contains NaOH alkali liquor, the concentration of the pretreatment is 60g/L, and the treatment time is 6 s; the concentration of the pretreatment ammonia sulfonic acid-containing acid liquid work station is 50g/L, and the treatment time is 3.5 s.

(2) And impact plating, wherein the impact plating is nickel sulfamate electroplating, the Ni content is 90g/L, the boric acid content is 35g/L, the nickel chloride content is 8g/L, the current density is 7ASD, and the thickness of an impact plating layer is 100 nm.

(3) And (3) sanding, wherein the sanding is electroplating of nickel sulfamate, Ni is 100g/L, boric acid is 30g/L, nickel chloride is 6g/L, and the current density is 9 ASD. The diamond D50 particle size in the sanding plating solution was 7.2 μm, and the diamond concentration was 2.0 g/L.

(4) And (3) consolidation, wherein the consolidation is nickel sulfamate electroplating, the Ni is 110g/L, the boric acid is 35g/L, the nickel chloride is 8g/L, and the current density is 9.5 ASD.

(5) And post-treatment, wherein the post-treatment comprises a normal-temperature pure water washing station and a drying station, and the drying temperature is 180 ℃. The alloy tungsten wire diamond wire saw with the specification of 43 mu m is prepared by taking up and winding, the sanding is uniform, the breaking force is more than or equal to 8.1N, the brittle failure frequency is 0.2, and the knotting breaking force accounts for more than or equal to 30 percent of the total breaking force.

The cutting process of the alloy tungsten wire diamond wire is applied as follows: the cutting size is 210 silicon rods, and the cutting process comprises the following steps: the cutting tension was 5.6N, the cutting tension ratio was not less than 63%, the groove depth of the guide cutter was 240 μm, the angle R of the guide cutter was 30 °, the pH of the cutting fluid was 5.0, and the cutting fluid supply was 1.7L. The single cutter line consumption is reduced by 10 percent, the wire breakage rate is reduced to be less than 2.0 percent, and the TTV mean value of the silicon chip is less than or equal to 10 mu m.

Example 1

The utility model provides a superfine high strength alloy tungsten filament diamond wire saw comprises alloy tungsten filament generating line and surperficial nickel layer metal consolidation diamond, the generating line is doping Re element alloy tungsten filament, nickel plating is sulfamic acid nickel system, diamond D50 particle size is 7.2 mu m.

Preparing an alloy tungsten wire bus:

(1) after the raw material tungsten powder is subjected to primary hydrogen reduction, the doped rhenium nitrate is stirred and mixed, so that the doping amount Re is 10.17 wt%.

(2) And (2) reducing the tungsten powder doped in the step (1) in a hydrogen reduction furnace at 700 ℃, carrying out secondary reduction in a hydrogen reduction furnace at 850 ℃, and carrying out acid pickling and material mixing to obtain the mixed alloy tungsten powder.

(3) And (3) carrying out isostatic pressing molding on the mixed powder obtained in the step (2) to obtain a semi-finished product with certain density and strength.

(4) Pre-sintering the semi-finished product obtained in the step (3) at the sintering temperature of 1200 ℃, and then performing vertical melting sintering at the sintering temperature of 2900 ℃.

(5) And (4) performing rotary swaging and cogging on the sample obtained in the step (4), and then performing annealing treatment in a hydrogen protection heating furnace, wherein the annealing temperature is 1100 ℃.

(6) And (4) continuously carrying out rotary swaging on the sample obtained in the step (5) to obtain the required diameter, and carrying out wire drawing, wherein the wire drawing die is a diamond die, the wire drawing lubricating liquid is graphite emulsion, and the black alloy tungsten wire (black wire for short) with the graphite emulsion attached to the surface is prepared, and the diameter of the black alloy tungsten wire is 44 microns.

(7) And (3) subjecting the 44-micron black wire sample obtained in the step (6) to electrolytic treatment, wherein the electrolyte is NAOH and the concentration is 100g/L, so as to prepare a 43-micron white alloy tungsten wire (white wire for short), the diameter of the tungsten wire is 43 +/-0.5 micron, the breaking force is not less than 7.5N, and the elastic modulus is 352 Gpa.

Preparing an alloy tungsten wire diamond wire:

(1) paying off an alloy tungsten wire bus, performing pretreatment and surface cleaning, wherein the concentration of the pretreatment NaOH-containing alkali liquor in a station is 60g/L, and the treatment time is 6 s; the concentration of the pretreatment ammonia sulfonic acid-containing acid liquid work station is 50g/L, and the treatment time is 3.5 s.

(5) And post-treatment, wherein the post-treatment comprises a normal-temperature pure water washing station and a drying station, and the drying temperature is 180 ℃. And (3) taking up and winding to prepare the alloy tungsten wire diamond wire saw with the specification of 43 microns, wherein the sanding is uniform, the breaking force is more than or equal to 8.2N, the brittle failure frequency is 0, and the knotting breaking force accounts for more than or equal to 45 percent of the total breaking force.

The cutting process of the alloy tungsten wire diamond wire is applied as follows:

the cutting size is 210 silicon rods, and the cutting process comprises the following steps: the cutting tension was 5.6N, the cutting tension ratio was not less than 63%, the groove depth of the guide cutter was 240 μm, the angle R of the guide cutter was 30 °, the pH of the cutting fluid was 5.0, and the cutting fluid supply was 1.7L. The single cutter line consumption is reduced by 10 percent, the wire breakage rate is reduced to be less than 2.0 percent, and the TTV mean value of the silicon chip is less than or equal to 10 mu m.

Example 2

The utility model provides a superfine high strength alloy tungsten filament diamond wire saw, comprises alloy tungsten filament generating line and surperficial nickel layer metal consolidation diamond, the generating line is doping La element alloy tungsten filament, the nickel plating is sulfamic acid nickel system, diamond D50 particle size is 7.2 mu m.

Preparing an alloy tungsten wire bus:

(1) after the raw material tungsten powder is subjected to primary hydrogen reduction, lanthanum nitrate is doped, stirred and mixed, so that the doping amount La is 13.32 wt%.

(6) And (4) continuously carrying out rotary swaging on the sample obtained in the step (5) to obtain the required diameter, and carrying out wire drawing, wherein the wire drawing die is a diamond die, the wire drawing lubricating liquid is graphite emulsion, and the black tungsten alloy wire with the graphite emulsion attached to the surface is prepared, and the diameter of the black tungsten alloy wire is 44 microns.

(7) And (4) subjecting the 44-micron black wire sample obtained in the step (6) to electrolytic treatment, wherein the electrolyte is NaOH and the concentration is 100g/L, so as to prepare the 43-micron white alloy tungsten wire, the diameter of the 43-micron white alloy tungsten wire is 43 +/-0.5 micron, the breaking force is not less than 7.8N, and the elastic modulus is 410 Gpa.

Preparing an alloy tungsten wire diamond wire:

(5) And post-treatment, wherein the post-treatment comprises a normal-temperature pure water washing station and a drying station, and the drying temperature is 180 ℃. And (3) taking up and winding to prepare the alloy tungsten wire diamond wire saw with the specification of 43 microns, wherein the sanding is uniform, the breaking force is more than or equal to 8.5N, the brittle failure frequency is 0, and the knotting breaking force accounts for more than or equal to 45 percent of the total breaking force.

The cutting process of the alloy tungsten wire diamond wire is applied as follows: the cutting size is 210 silicon rods, and the cutting process comprises the following steps: the cutting tension was 5.6N, the cutting tension ratio was not less than 63%, the groove depth of the guide cutter was 240 μm, the angle R of the guide cutter was 30 °, the pH of the cutting fluid was 5.0, and the cutting fluid supply was 1.7L. The single cutter line consumption is reduced by 13 percent, the wire breakage rate is reduced to less than 1.5 percent, and the TTV mean value of the silicon chip is less than or equal to 10 mu m.

Example 3

The utility model provides a superfine high strength alloy tungsten filament diamond wire saw comprises alloy tungsten filament generating line and surperficial nickel layer metal consolidation diamond, the generating line is doping Re, La element alloy tungsten filament, the nickel plating is the nickel sulfamic acid nickel system, diamond D50 particle size is 7.2 mu m.

Preparing an alloy tungsten wire bus:

(1) after the raw material tungsten powder is subjected to primary hydrogen reduction, doping rhenium nitrate and lanthanum nitrate are stirred and mixed, so that the doping amount Re is 10.17 wt% and the doping amount La is 13.32 wt%.

(6) And (4) continuously carrying out rotary swaging on the sample obtained in the step (5) to obtain the required diameter, and carrying out wire drawing, wherein the wire drawing die is a diamond die, the wire drawing lubricating liquid is graphite emulsion, and the black alloy tungsten wire with the graphite emulsion attached to the surface is prepared, and the diameter of the black alloy tungsten wire is 44 microns.

(7) And (4) subjecting the 44-micron black wire sample obtained in the step (6) to electrolytic treatment, wherein the electrolyte is NAOH and the concentration is 100g/L, so as to prepare the 43-micron white wire alloy tungsten wire, the diameter of the 43-micron white wire alloy tungsten wire is 43 +/-0.5 microns, the breaking force is not less than 7.9N, and the elastic modulus is 420 Gpa.

Preparation of diamond wire:

(1) paying off an alloy tungsten wire bus, performing pretreatment and surface cleaning, wherein the pretreatment contains an NaOH solution work station, the concentration is 60g/L, and the treatment time is 6 s; the concentration of the pretreatment ammonia sulfonic acid-containing acid liquid work station is 50g/L, and the treatment time is 3.5 s.

(5) And post-treatment, wherein the post-treatment comprises a normal-temperature pure water washing station and a drying station, and the drying temperature is 180 ℃. And (3) taking up and winding to prepare the alloy tungsten wire diamond wire saw with the specification of 43 microns, wherein the sanding is uniform, the breaking force is more than or equal to 8.8N, the brittle failure frequency is 0, and the knotting breaking force accounts for more than or equal to 45 percent of the total breaking force.

The cutting process of the alloy tungsten wire diamond wire is applied as follows: the cutting size is 210 silicon rods, and the cutting process comprises the following steps: the cutting tension was 5.6N, the cutting tension ratio was not less than 63%, the groove depth of the guide cutter was 240 μm, the angle R of the guide cutter was 30 °, the pH of the cutting fluid was 5.0, and the cutting fluid supply was 1.7L. The single cutter line consumption is reduced by 15 percent, the wire breakage rate is reduced to less than 1 percent, and the TTV mean value of the silicon chip is less than or equal to 10 mu m.

Example 4

The utility model provides a superfine high strength alloy tungsten filament diamond wire saw comprises alloy tungsten filament generating line and surperficial nickel layer metal consolidation diamond, the generating line is doping Re, La element alloy tungsten filament, the nickel plating is the nickel sulfamic acid nickel system, diamond D50 particle size is 6.5 mu m.

Preparing an alloy tungsten wire bus:

(4) Pre-sintering the semi-finished product in the step (3) at the sintering temperature of 1200 ℃, and then performing vertical melting sintering at the sintering temperature of 2900 ℃.

(6) And (4) continuously carrying out rotary swaging on the sample obtained in the step (5) to obtain the required diameter, and carrying out wire drawing, wherein the wire drawing die is a diamond die, the wire drawing lubricating liquid is graphite emulsion, and the black wire with the graphite emulsion attached to the surface is prepared, and the diameter of the black wire is 41 micrometers.

(7) And (4) subjecting the 41-micron black wire sample obtained in the step (6) to electrolytic treatment, wherein the electrolyte is NAOH and the concentration is 100g/L, so as to prepare the 40-micron white wire alloy tungsten wire, the diameter of the wire is 40 +/-0.5 micron, the breaking force is not less than 7.0N, and the elastic modulus is 371 Gpa.

Preparing an alloy tungsten wire diamond wire:

(1) paying off an alloy tungsten wire bus, performing pretreatment and surface cleaning, wherein the pretreatment contains an NAOH alkali liquor station, the concentration is 40g/L, and the treatment time is 6 s; the concentration of the pretreatment ammonia sulfonic acid-containing acid liquid work station is 40g/L, and the treatment time is 3.5 s.

(2) And impact plating, wherein the impact plating is nickel sulfamate electroplating, the Ni content is 90g/L, the boric acid content is 35g/L, the nickel chloride content is 8g/L, the current density is 6.5ASD, and the thickness of an impact plating layer is 90 nm.

(3) And (3) sanding, wherein the sanding is electroplating of nickel sulfamate, Ni is 100g/L, boric acid is 30g/L, nickel chloride is 6g/L, and the current density is 8.0 ASD. The diamond D50 particle size in the sanding plating solution was 6.5 μm, and the diamond concentration was 1.8 g/L.

(4) And (3) consolidation, wherein the consolidation is nickel sulfamate electroplating, the Ni is 110g/L, the boric acid is 35g/L, the nickel chloride is 8g/L, and the current density is 8.0 ASD.

(5) And post-treatment, wherein the post-treatment comprises a normal-temperature pure water washing station and a drying station, and the drying temperature is 180 ℃. The alloy tungsten wire diamond wire saw with the specification of 40 mu m is prepared by taking up and winding, the sanding is uniform, the breaking force is more than or equal to 7.8N, the brittle failure frequency is 0, and the knotting breaking force accounts for more than or equal to 43 percent of the total breaking force.

The cutting process of the alloy tungsten wire diamond wire is applied as follows: the cutting size is 210 silicon rods, and the cutting process comprises the following steps: the cutting tension is 4.7N, the cutting tension is more than or equal to 60%, the groove depth of the cutting guide wheel is 240 μm, the R angle of the guide wheel is 28 °, the PH of the cutting fluid is 5.0, and the supply amount of the cutting fluid is 1.7L. The single cutter line consumption is reduced by 12 percent, the wire breakage rate is reduced to less than 1.5 percent, and the TTV mean value of the silicon chip is less than or equal to 10 mu m.

Example 5

The utility model provides a superfine high strength alloy tungsten filament diamond wire saw comprises alloy tungsten filament generating line and surperficial nickel layer metal consolidation diamond, the generating line is doping Re, La element alloy tungsten filament, the nickel plating is the nickel sulfamic acid nickel system, diamond D50 particle size is 7.5 mu m.

Preparing an alloy tungsten wire bus:

(1) after the raw material tungsten powder is subjected to primary hydrogen reduction, doping rhenium nitrate and lanthanum nitrate are stirred and mixed, so that the doping amount Re is 10.17 wt% and the doping amount La is 13.32 wt%. .

(6) And (4) continuously carrying out rotary swaging on the sample obtained in the step (5) to obtain the required diameter, and carrying out wire drawing, wherein the wire drawing die is a diamond die, the wire drawing lubricating liquid is graphite emulsion, and the black wire with the graphite emulsion attached to the surface is prepared, and the diameter of the black wire is 38 micrometers.

(7) And (4) subjecting the 38-micron black wire sample obtained in the step (6) to electrolytic treatment, wherein the electrolyte is NAOH and the concentration is 100g/L, so as to prepare a 37-micron white alloy tungsten wire, the diameter of the tungsten wire is 37 +/-0.5 micron, the breaking force is more than or equal to 6.2N, and the elastic modulus is 356 Gpa.

Preparing an alloy tungsten wire diamond wire:

(1) paying off an alloy tungsten wire bus, performing pretreatment and surface cleaning, wherein the pretreatment contains an NAOH alkali liquor station, the concentration is 40g/L, and the treatment time is 4.5 s; the concentration of the pretreatment ammonia sulfonic acid-containing acid liquid work station is 40g/L, and the treatment time is 3.0 s.

(2) And impact plating, wherein the impact plating is nickel sulfamate electroplating, the Ni content is 90g/L, the boric acid content is 35g/L, the nickel chloride content is 8g/L, the current density is 7.5ASD, and the thickness of an impact plating layer is 160 nm.

(3) And (3) sanding, wherein the sanding is electroplating of nickel sulfamate, Ni is 100g/L, boric acid is 30g/L, nickel chloride is 6g/L, and the current density is 6.7 ASD. The diamond D50 particle size in the sanding plating solution was 6.5 μm, and the diamond concentration was 1.5 g/L.

(4) And (3) consolidation, wherein the consolidation is nickel sulfamate electroplating, the Ni is 110g/L, the boric acid is 35g/L, the nickel chloride is 8g/L, and the current density is 7.5 ASD.

(5) And post-treatment, wherein the post-treatment comprises a normal-temperature pure water washing station and a drying station, and the drying temperature is 180 ℃. The alloy tungsten wire diamond wire saw with the specification of 37 mu m is prepared by taking up and winding, the sanding is uniform, the breaking force is more than or equal to 6.9N, the brittle failure frequency is 0, and the knotting breaking force accounts for more than or equal to 38 percent of the total breaking force.

the cutting size is 182 silicon rods, and the cutting process comprises the following steps: the cutting tension was 4.1N, the cutting tension ratio was not less than 53%, the groove depth of the guide roller was 240 μm, the R angle of the guide roller was 25 °, the PH of the cutting fluid was 5.0, and the cutting fluid supply was 1.7L. The single cutter line consumption is reduced by 10 percent, the line breakage rate is reduced to less than 1.5 percent, and the TTV mean value of the silicon chip is less than or equal to 10 mu m.

Example 6

Preparing an alloy tungsten wire bus:

(1) after the raw material tungsten powder is subjected to primary hydrogen reduction, doping rhenium nitrate and lanthanum nitrate, and stirring and mixing to ensure that the doping amount Re is 3 wt% and the doping amount La is 15 wt%.

(5) And (4) performing rotary swaging and cogging on the sample in the step (4), and then performing annealing treatment in a hydrogen protection heating furnace, wherein the annealing temperature is 1100 ℃.

(6) And (4) continuously carrying out rotary swaging on the sample obtained in the step (5) to obtain the required diameter, and carrying out wire drawing, wherein the wire drawing die is a diamond die, the wire drawing lubricating liquid is graphite emulsion, and the black wire with the graphite emulsion attached to the surface is prepared, and the diameter of the black wire is 44 microns.

(7) And (3) subjecting the 44-micron black wire sample obtained in the step (6) to electrolytic treatment, wherein the electrolyte is NAOH and the concentration is 100g/L, so that the 43-micron white wire alloy tungsten wire is prepared, the diameter of the wire is 43 +/-0.5 micron, the breaking force is not less than 7.7N, and the elastic modulus is 375 Gpa.

Preparation of diamond wire:

(5) And post-treatment, wherein the post-treatment comprises a normal-temperature pure water washing station and a drying station, and the drying temperature is 180 ℃. And (3) taking up and winding to prepare the alloy tungsten wire diamond wire saw with the specification of 43 microns, wherein the sanding is uniform, the breaking force is more than or equal to 8.5N, the brittle failure frequency is 0, and the knotting breaking force accounts for more than or equal to 42% of the total breaking force.

The cutting process of the alloy tungsten wire diamond wire is applied as follows: the cutting size is 210 silicon rods, and the cutting process comprises the following steps: the cutting tension is 5.6N, the cutting tension ratio is more than or equal to 66.6%, the groove depth of the cutting guide wheel is 240 μm, the R angle of the guide wheel is 30 degrees, the PH of the cutting fluid is 5.0, and the supply amount of the cutting fluid is 1.7L. The single cutter line consumption is reduced by 10 percent, the line breakage rate is reduced to less than 1.5 percent, and the TTV mean value of the silicon chip is less than or equal to 11 mu m.

Example 7

Preparing an alloy tungsten wire bus:

(1) after the raw material tungsten powder is subjected to primary hydrogen reduction, doping rhenium nitrate and lanthanum nitrate are stirred and mixed, so that the doping amount Re is 20 wt% and the doping amount La is 2.5 wt%.

(7) And (3) subjecting the 44-micron black wire sample obtained in the step (6) to electrolytic treatment, wherein the electrolyte is NAOH and the concentration is 100g/L, so that the 43-micron white wire alloy tungsten wire is prepared, the diameter of the wire is 43 +/-0.5 micron, the breaking force is not less than 7.5N, and the elastic modulus is 368 Gpa.

Preparation of diamond wire:

(5) And post-treatment, wherein the post-treatment comprises a normal-temperature pure water washing station and a drying station, and the drying temperature is 180 ℃. The alloy tungsten wire diamond wire saw with the specification of 43 mu m is prepared by taking up and winding, the sanding is uniform, the breaking force is more than or equal to 8.3N, the brittle failure frequency is 0, and the knotting breaking force accounts for more than or equal to 41 percent of the total breaking force.

The cutting process of the alloy tungsten wire diamond wire is applied as follows: the cutting size is 210 silicon rods, and the cutting process comprises the following steps: the cutting tension is 5.6N, the cutting tension is more than or equal to 60 percent, the groove depth of the cutting guide wheel is 240 mu m, the R angle of the guide wheel is 30 degrees, the PH value of the cutting fluid is 5.0, and the supply amount of the cutting fluid is 1.7L. The single cutter line consumption is reduced by 12.5%, the line breakage rate is reduced to less than 1.5%, and the TTV mean value of the silicon chip is less than or equal to 13 mu m.

Example 8

Preparing an alloy tungsten wire bus:

(1) after the raw material tungsten powder is subjected to primary hydrogen reduction, doping rhenium nitrate and lanthanum nitrate are stirred and mixed, so that the doping amount Re is 8.3 wt% and the doping amount La is 10 wt%.

(7) And (3) subjecting the 44-micron black wire sample obtained in the step (6) to electrolytic treatment, wherein the electrolyte is NAOH and the concentration is 100g/L, so that the 43-micron white wire alloy tungsten wire is prepared, the diameter of the wire is 43 +/-0.5 micron, the breaking force is not less than 7.8N, and the elastic modulus is 390 Gpa.

Preparation of diamond wire:

(5) And post-treatment, wherein the post-treatment comprises a normal-temperature pure water washing station and a drying station, and the drying temperature is 180 ℃. And (3) taking up and winding to prepare the alloy tungsten wire diamond wire saw with the specification of 43 microns, wherein the sanding is uniform, the breaking force is more than or equal to 8.6N, the brittle failure frequency is 0, and the knotting breaking force accounts for more than or equal to 45 percent of the total breaking force.

The cutting process of the alloy tungsten wire diamond wire is applied as follows: the cutting size is 210 silicon rods, and the cutting process comprises the following steps: the cutting tension is 5.6N, the cutting tension is more than or equal to 60 percent, the groove depth of the cutting guide wheel is 240 mu m, the R angle of the guide wheel is 30 degrees, the PH value of the cutting fluid is 5.0, and the supply amount of the cutting fluid is 1.7L. The single cutter line consumption is reduced by 13 percent, the line breakage rate is reduced to less than 1.0 percent, and the TTV mean value of the silicon chip is less than or equal to 10 mu m.

The tungsten wire alloy diamond wire saw parameters and the customer cutting verification data of the above comparative example and 8 examples are shown in tables 1 and 2, respectively.

TABLE 1 Diamond linear energy parameters obtained in examples 1 to 8

Table 2 customer application performance of the products of examples 1-8.

As can be seen from the data in tables 1 and 2:

the invention relates to a method for preparing an alloy bus by doping metal elements: re and La can be doped according to certain content to prepare alloy tungsten wire bus with higher strength than carbon steel bus of the same specification, low brittle failure frequency, high elastic modulus and strong corrosion resistance, and the alloy tungsten wire bus has obvious reduction effect on wire breakage rate in cutting. In the process of manufacturing the diamond wire, the alloy tungsten wire bus has obvious help on the sand feeding capacity and the sand feeding uniformity by increasing the thickness of a plating layer of impact plating, the production line speed is obviously increased compared with that of a common carbon steel bus, and the manufactured alloy tungsten wire diamond fretsaw can continue the bus performance and has the mechanical characteristics of low brittle failure times, high breaking force and the like. In the application of photovoltaic silicon wafer cutting, the cutting efficiency is obviously improved and the single linear loss and the TTV mean value of the silicon wafer are obviously reduced by optimizing a specific cutting technology (comprising the depth of a guide wheel groove, the change of an R angle, the downward regulation of the PH of a cutting liquid and the increase of the cutting tension load proportion).

The foregoing are merely embodiments of the present invention and it should be noted that the present invention extends to any novel feature or any novel combination disclosed herein and any novel method or process steps or any novel combination disclosed herein for the field of diamond wire saw manufacture.

Claims

1. The tungsten wire is characterized in that 0.03-20% of Re and/or 0.01-15% of La are/is doped in the tungsten wire, the diameter of the tungsten wire is 30-50 mu m, the strength is not less than 5100Mpa, and the elastic modulus is 350-450 Gpa.

2. The tungsten wire alloy wire according to claim 1, wherein the tungsten wire is doped with 3 to 20% by weight of Re and/or 2.5 to 15% by weight of La.

3. A method of making the tungsten wire alloy wire of claim 1 or 2 comprising the steps of:

and step 3: carrying out primary hydrogen reduction on the mixed tungsten powder obtained in the step 2 in a 700 ℃ hydrogen reduction furnace, and carrying out secondary hydrogen reduction in a 850 ℃ hydrogen reduction furnace to obtain mixed alloy tungsten powder;

and 7: and (4) continuously and rotatably forging the product obtained in the step (6) to prepare an alloy tungsten rod with the diameter of 2-3mm, uniformly coating the surface of the alloy tungsten rod with graphite emulsion, and drawing the alloy tungsten rod to a tungsten wire alloy wire with the diameter of 30-50 microns through a diamond die.

4. The method for preparing a tungsten wire alloy wire according to claim 3, wherein the acid cleaning and impurity removal in step 1 are performed using a mixed solution of sulfamic acid and hydrochloric acid, wherein the concentration of sulfamic acid is 50g/L and the concentration of hydrochloric acid is 60 ml/L.

5. The method for preparing a tungsten wire alloy according to claim 3, wherein the isostatic pressing in step 3 is carried out at a process parameter of 150 to 230MPa for 30 to 60 min.

6. The method of manufacturing a tungsten wire alloy wire according to claim 3, wherein the diamond die in step 7 is a 7.5 ° diamond die, and the graphite emulsion is a graphite nanopowder having a D50 ═ 0.2 μm.

7. A diamond wire saw made of the tungsten wire alloy wire of claim 1 or 2 is characterized by comprising a tungsten wire alloy bus, a pre-plated nickel layer, a sand nickel layer and a sand nickel layer from inside to outside in sequence, wherein the thickness of the pre-plated nickel layer is 30-500 nm, the diameter of the diamond wire saw is 45-65 μm, and the breaking tension is 6.5-11N.

8. A method of making the diamond wire saw of claim 7, comprising the steps of:

9. The use method of the diamond wire saw according to claim 7, characterized in that the tungsten wire alloy diamond wire saw is wound to a grooving guide wheel under a tension of 3.5-6.0N to form a running dense wire net with a speed of 600-2100 m/min, a silicon rod to be cut is pressed into the dense wire net at a table speed of 200-2100 mm/min under the cooling of cutting liquid, and the silicon rod is cut into silicon wafers with consistent thickness by using the cutting force of the tungsten wire alloy diamond wire saw; the length of the wire mesh is 4.5-8.0 km, the diameter of the slotted guide wheel is 190-210 mm, the included angle of the slot is 20-40 degrees, the slot depth of the guide wheel is 150-240 mu m, and the R angle of the slot of the guide wheel is 20-45 degrees; the cutting fluid is a cutting water solution with high organic matter COD content, the PH value of the cutting water solution is controlled to be 3.5-6.5, the cutting process table speed is 200-2100 mm/min, and the linear speed is 600-2100 m/min.

10. The method of using the diamond wire saw as set forth in claim 9, wherein the grooved guide wheel is two-axis or three-axis.