CN215947378U - Tungsten alloy wire - Google Patents
Tungsten alloy wire Download PDFInfo
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- CN215947378U CN215947378U CN202121648337.5U CN202121648337U CN215947378U CN 215947378 U CN215947378 U CN 215947378U CN 202121648337 U CN202121648337 U CN 202121648337U CN 215947378 U CN215947378 U CN 215947378U
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Abstract
The utility model relates to the technical field of tungsten alloy materials, in particular to a tungsten alloy wire. The tungsten alloy wire sequentially comprises a core body and a composite layer coated on the surface of the core body from inside to outside; the wire diameter of the tungsten alloy wire is 100 mu m or less; the core body is a metal wire made of tungsten or tungsten alloy; the composite layer sequentially comprises an oxide layer and a graphite emulsion layer from inside to outside; the thickness of the composite layer is 0.2-5 microns, the thickness ratio of the oxide layer to the composite layer is 55-75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25-45%. The utility model provides a tungsten alloy wire, which can effectively reduce wire breakage and die consumption through a composite layer structure on the surface of the tungsten alloy wire. In addition, the tungsten alloy wire has small wire diameter and high mechanical properties such as tensile strength and elastic limit strength.
Description
Technical Field
The utility model relates to the technical field of tungsten alloy materials, in particular to a tungsten alloy wire.
Background
High carbon steel wire, tungsten wire, etc. are known as materials having a certain high strength and hardness. However, the tensile strength of the conventional high carbon steel wire is generally below 4200MPa, but the diameter thereof is larger than 50 μm and has reached the processing limit, and the tensile strength cannot be improved by processing the steel wire into a smaller diameter.
The tensile strength of the conventional tungsten wire is generally below 4000MPa, the strength of the conventional tungsten wire is improved by further thinning or alloy strengthening, but with the improvement of the strength of the tungsten wire, the probability of generation of defects such as processing cracks and the like is increased, so that the performance of the wire is influenced, the wire breakage probability of the material is obviously increased, the loss of a die is obviously increased, and finally, the batch production of the high-strength and high-toughness tungsten wire is difficult to realize.
In the applications of high-hardness materials, such as sapphire and silicon carbide which are semiconductor materials, silicon wafers and magnetic materials, and cables or ropes drawn by high-precision instruments and high-temperature furnaces, a wire rod with higher strength and high toughness is urgently needed in the market, so that the wire rod can meet various practical requirements in the field of practical application. Therefore, the problems of increased processing crack defects, increased wire breakage rate and increased die loss in the process of improving the strength of the wire rod are urgently needed to be solved in the field.
SUMMERY OF THE UTILITY MODEL
In order to solve the problems: the mechanical properties such as strength and the like of the conventional tungsten wire are difficult to meet the use requirements, for example, the tungsten wire strength is improved by thinning or alloy strengthening, and the defects of increased wire processing cracks, increased wire breakage rate, increased die loss and the like exist in the process, so that the tungsten wire strength is difficult to realize.
The utility model provides a tungsten alloy wire, which sequentially comprises a core body and a composite layer coated on the surface of the core body from inside to outside; the wire diameter of the tungsten alloy wire is 100 mu m or less; the core body is a metal wire made of tungsten or tungsten alloy; the thickness of the composite layer is 0.2-5 microns, the thickness ratio of the oxide layer to the composite layer is 55-75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25-45%.
Further, in some embodiments, the core is a metal wire composed of an alloy of tungsten and a rare earth oxide, the wire diameter of the tungsten alloy wire is 100 μm or less, and the tensile strength of the tungsten alloy wire is 3800MPa or more.
Further, in some embodiments, the wire diameter of the tungsten alloy wire is 60 μm to 100 μm, and the thickness of the composite layer is 0.45 μm to 5 μm.
Further, in some embodiments, the core is a metal wire made of an alloy of tungsten and a rare earth oxide, the wire diameter of the tungsten alloy wire is 60 μm or less, the diameter of the push-pull core wire is 350 μm or less, the proof stress is 2500MPa or more, and the tensile strength is 4200MPa or more.
Further, in some embodiments, the wire diameter of the tungsten alloy wire is 40 μm to 60 μm, and the thickness of the composite layer is 0.25 μm to 2.5 μm.
Further, in some embodiments, the core is a metal wire composed of an alloy of tungsten and a rare earth oxide, the tungsten alloy wire having a wire diameter of 40 μm or less, a tensile strength of 4800MPa or more, and an proof stress of 3000MPa or more.
Further, in some embodiments, the wire diameter of the tungsten alloy wire is 25 μm to 40 μm, and the thickness of the composite layer is 0.25 μm to 2.0 μm.
Further, in some embodiments, the core is a metal wire composed of an alloy of tungsten and a rare earth oxide, the tungsten alloy wire has a wire diameter of 25 μm or less, a tensile strength of 5000MPa or more, and an proof stress of 3000MPa or more.
Further, in some embodiments, the tungsten alloy wire has a wire diameter of 25 μm or less, and the composite layer has a thickness of 0.2 μm to 1.25 μm.
Further, in some embodiments, the weight ratio of the composite layer to the tungsten alloy wire is 0.5% to 3.5%.
Compared with the prior art, the utility model has the following beneficial effects:
according to the tungsten alloy wire rod provided by the utility model, the wire breakage and the die consumption can be effectively reduced through the composite layer structure with a certain thickness on the surface of the tungsten alloy wire rod. In addition, the tungsten alloy wire rod provided by the utility model is small in wire diameter and has high tensile strength, elastic limit strength and toughness.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic perspective view of a tungsten alloy wire according to an embodiment of the present invention;
FIG. 2 is a first cross-sectional view taken along line A-A of FIG. 1;
FIG. 3 is a partial enlarged view of FIG. 2 at B;
FIG. 4 is a schematic sectional view A-A of FIG. 1;
fig. 5 is a schematic structural diagram of a device for push-pull toughness detection according to an embodiment of the present invention.
Reference numerals:
100 tungsten alloy wire 110 core 120 oxide layer
130 graphite emulsion layer 340 heart line 310 sample dish
320 take-up spool 330 weight
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it should be noted that the terms "center", "longitudinal", "lateral", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplicity of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
The utility model provides a tungsten alloy wire 100, which sequentially comprises a core body 110 and a composite layer coated on the surface of the core body 110 from inside to outside; the wire diameter of the tungsten alloy wire 100 is 100 μm or less; the core body is a metal wire made of tungsten or tungsten alloy; the composite layer sequentially comprises an oxide layer 120 and a graphite emulsion layer 130 from inside to outside; the thickness of the composite layer is 0.2-5 microns, the thickness ratio of the oxide layer to the composite layer is 55-75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25-45%.
Specifically, as shown in fig. 1-3, the composite layer is attached to the core 110 in a wrapping manner and extends over the outer circumferential surface of the core 110; the tungsten alloy wire 100 sequentially comprises a core 110, an oxide layer 120 and a graphite emulsion layer 130 from inside to outside. The expression "from inside to outside" herein means from the axial center of the tungsten alloy wire 100 to the outer circumferential surface of the tungsten alloy wire 100 in the radial direction.
The surface of the tungsten alloy wire 100 provided by the utility model is provided with a composite layer, the thickness of the composite layer is controlled to be 0.2-5 μm, the thickness ratio of the oxide layer to the composite layer is 55-75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25-45%; the composite layer with the lubricating effect can effectively reduce broken wires and reduce die consumption, particularly, the graphite emulsion layer 130 in the composite layer is arranged on the outermost layer and mainly plays a lubricating effect, the oxide layer 120 is arranged on the surface of the core body 110, the graphite emulsion layer 130 is attached to the surface of the core body, and the graphite emulsion layer 130 can be uniformly and firmly attached to the wires through the oxide layer 120 so as to fully play the lubricating effect. In general, the composite layer structure on the surface of the tungsten alloy wire 100 can reduce the generation of wire processing cracks, remarkably reduce wire breakage and reduce abrasion, and realize smooth diameter reduction of the tungsten alloy wire 100, so that the tungsten alloy wire 100 has small wire diameter, high tensile strength, elastic limit strength and toughness.
The thicknesses of the composite layer, the graphite emulsion layer 130 and the oxide layer 120 are set as follows: on one hand, when the thickness of the composite layer is too small and the thickness of the graphite emulsion layer 130 is relatively small, the graphite emulsion layer 130 cannot exert good lubricating effect, so that the probability of generating processing cracks is increased, the wire breakage rate is increased, the die consumption is increased, and the mass production of the tungsten alloy wire 100 with high strength and high toughness and small diameter is difficult to realize; when the thickness of the composite layer is too large, the wire rod is heated and cannot be thoroughly heated in the process of hot processing of the wire rod, namely, heat cannot be sufficiently transmitted to the inside from the outside, so that the difference of the processing quality of the inner part and the outer part of the wire rod is large, and the defects of wire rod diameter fluctuation and internal crack are easily generated. On the other hand, the thickness ratio of the oxide layer 120 and the graphite emulsion layer 130 in the composite layer is limited, and if the oxide layer 120 is too thin, the graphite emulsion layer 130 cannot be uniformly coated on the surface, so that the lubrication effect is poor, the yarn breakage rate is high, and the die loss is increased; as shown in fig. 3, since the tungsten alloy wire 100 is of a wire rod-shaped structure, the oxide layer 120 on the tungsten alloy wire 100 changes from a dense structure to a loose structure from inside to outside, and the outermost part of the oxide layer 120 is the loosest, wherein the graphite emulsion layer 130 is in immersion contact with the oxide layer 120, and when the oxide layer 120 is too thick, the outer loose part of the graphite emulsion layer 130 is thicker, which easily causes peeling-off of the graphite emulsion layer 130 during processing, resulting in high wire breakage rate and increased die loss.
The utility model also provides a preparation method of the tungsten alloy wire 100, which comprises the following steps: (1) performing multi-pass rotary swaging on a metal material composed of tungsten or tungsten alloy, namely the core body 110 material; (2) and (2) repeating the core body 110 material obtained in the step (1) for a plurality of times to perform a wire drawing process: sequentially performing a wire unwinding step, a graphite emulsion coating step, a heating and drying step and a single-pass or multi-pass drawing step, and repeating the steps for multiple times until a wire rod with a certain wire diameter specification is obtained; (3) carrying out oxidation burning loss on the wire rod obtained after the wire drawing process treatment, namely carrying out oxidation burning loss on the wire rod before the final drawing step of preparing the expected wire diameter; (3) and performing a final wire drawing process: and (4) sequentially performing a graphite emulsion coating step, a heating and drying step and a multi-pass drawing step on the wire rod obtained in the step (3) to obtain the tungsten alloy wire rod 100 with the wire diameter specification required finally. In addition, in some embodiments, in the middle of the step (2) repeating the wire drawing process for a plurality of times, the wire rod after the wire drawing step is finished can be selected to be subjected to oxidation burning loss treatment;
specifically, in the method for producing the tungsten alloy wire 100, the drawing reduction amount per pass in the drawing step is controlled, for example, the reduction amount of the cross-sectional area of a wire rod of 25 to 60 μm per pass is controlled to 10 to 15%, and the reduction amount of the cross-sectional area of a wire rod of 60 to 100 μm per pass is controlled to 13 to 18%; the particle size of the selected lubricant graphite emulsion is controlled to be 1-3 mu m, and the specific gravity of the graphite emulsion is controlled to be 1.01-1.05 g/cm; the oxide layer 120 is formed through an intermediate oxidation burning loss process, the oxidation burning loss temperature is selected according to different wire diameter specifications, and the oxide layer 120 with a certain thickness is formed on the surface by controlling the oxidation burning loss temperature, so that the uniform coating of the graphite emulsion is facilitated; for example, the wire diameter of the wire is more than 1.7mm, and the oxidation burning loss temperature is 1100-1500 ℃; the wire diameter of the wire rod is between 0.39 and 1.7mm, the oxidation burning loss temperature is between 1000 and 1400 ℃; the wire diameter of the wire is 0.1 mm-0.39 mm, and the oxidation burning loss is 900 ℃ -1300 ℃; the wire diameter of the wire rod is less than 0.1mm, and the oxidation burning loss temperature is 800-1200 ℃;
in the method for preparing the tungsten alloy wire 100, the wire drawing and the oxidation burning process are matched to prepare the tungsten alloy wire 100 so that the surface of the tungsten alloy wire 100 has the composite layer structure, and the control process of the size of the composite layer mainly comprises the steps of before finishing, namely the control of the oxidation burning temperature in the step (3) and the control of the single-pass cross-sectional area reduction of the wire in the final drawing step in the step (4).
Preferably, in some embodiments, the weight ratio of the composite layer to the tungsten alloy wire 100 is 0.5% to 3.5%.
Preferably, in some embodiments, the wire diameter of the tungsten alloy wire 100 is 60 μm to 100 μm, the thickness of the composite layer is 0.45 μm to 5 μm, the thickness ratio of the oxide layer to the composite layer is 55% to 75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25% to 45%; preferably, in some embodiments, the wire diameter of the tungsten alloy wire 100 is 60 μm to 80 μm, the thickness of the composite layer may be 0.45 μm to 2.2 μm, the thickness ratio of the oxide layer to the composite layer is 55% to 75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25% to 45%; the wire diameter of the tungsten alloy wire 100 is 80-100 μm, the thickness of the composite layer can be 0.6-5 μm, the thickness ratio of the oxide layer to the composite layer is 55-75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25-45%;
for example, the wire diameter of the tungsten alloy wire 100 is 100 μm, the thickness of the composite layer is 1.2 μm to 5 μm, the thickness of the oxide layer 120 is 0.9 μm to 2.7 μm, the thickness ratio of the oxide layer to the composite layer is 55% to 75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25% to 45%; for another example, the wire diameter of the tungsten alloy wire 100 is 80 μm, the thickness of the composite layer is 0.6 μm to 2.2 μm, the thickness of the oxide layer 120 is 0.75 μm to 1.15 μm, the thickness ratio of the oxide layer to the composite layer is 55% to 75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25% to 45%; for another example, the wire diameter of the tungsten alloy wire 100 is 60 μm, the thickness of the composite layer is 0.45 μm to 1.9 μm, the thickness of the oxide layer 120 is 0.35 μm to 1.05 μm, the thickness ratio of the oxide layer to the composite layer is 55% to 75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25% to 45%;
preferably, in some embodiments, the wire diameter of the tungsten alloy wire 100 is 40 μm to 60 μm, the thickness of the composite layer is 0.25 μm to 2.5 μm, the thickness ratio of the oxide layer to the composite layer is 55% to 75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25% to 45%; preferably, in some embodiments, the wire diameter of the tungsten alloy wire 100 is 40 μm to 50 μm, the thickness of the composite layer may be 0.25 μm to 1.85 μm, the thickness of the oxide layer 120 is 0.18 μm to 1.00 μm, the thickness ratio of the oxide layer to the composite layer is 55% to 75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25% to 45%; the wire diameter of the tungsten alloy wire 100 is 50-60 μm, the thickness of the composite layer can be 0.3-1.9 μm, the thickness of the oxide layer 120 is 0.25-1.00 μm, the thickness ratio of the oxide layer to the composite layer is 55-75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25-45%;
for example, the wire diameter of the tungsten alloy wire 100 is 50 μm, the thickness of the composite layer is 0.30 to 1.85 μm, the thickness of the oxide layer 120 is 0.2 to 1.00 μm, the thickness ratio of the oxide layer to the composite layer is 55 to 75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25 to 45%; for another example, the wire diameter of the tungsten alloy wire 100 is 40 μm, the thickness of the composite layer is 0.25 to 1.45 μm, the thickness of the oxide layer 120 is 0.18 to 0.80 μm, the thickness ratio of the oxide layer to the composite layer is 55 to 75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25 to 45%;
preferably, in some embodiments, the wire diameter of the tungsten alloy wire 100 is 25 μm to 40 μm, the thickness of the composite layer is 0.25 μm to 2.0 μm, the thickness ratio of the oxide layer to the composite layer is 55% to 75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25% to 45%; preferably, in some embodiments, the wire diameter of the tungsten alloy wire 100 is 25 μm to 40 μm, the thickness of the composite layer may be 0.25 μm to 1.7 μm, the thickness ratio of the oxide layer to the composite layer is 55% to 75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25% to 45%; preferably, in some embodiments, the wire diameter of the tungsten alloy wire 100 is 25 μm to 40 μm, the thickness of the composite layer may be 0.25 μm to 1.45 μm, the thickness ratio of the oxide layer to the composite layer is 55% to 75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25% to 45%;
preferably, in some embodiments, the wire diameter of the tungsten alloy wire 100 is 25 μm or less, the thickness of the composite layer is 0.2 μm to 1.25 μm, the thickness ratio of the oxide layer to the composite layer is 55% to 75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25% to 45%; in the preferred embodiment, the thickness of the composite layer structure of the tungsten alloy wire 100 with different wire diameter specifications is further optimized to further improve the performance of the tungsten alloy wire 100.
The thickness test method herein is: 1. preparing a sample: preparing a sample (Ionmilling) by using a section ion polisher, firstly fixing a metal wire in a plane by using glue, and then putting the metal wire into ion polisher equipment to bombard the section by using Ga ions to obtain a region to be measured; 2. and (3) observation and measurement: and (3) acquiring a section of the sample to be measured, then shooting by using a scanning electron microscope to acquire the section shown in the figure 2-4, measuring the thicknesses of the composite layer, the oxide layer 120 and the graphite emulsion layer 130 at a plurality of positions, and taking the average value of the thicknesses. Wherein the oxide layer 120 and the graphite emulsion layer 130 are distinguished in determining their material compositions, the main constituent material of the oxide layer 120 being an oxide, for example in some embodiments the oxide contains only tungsten trioxide, and the oxide can be derived by X-ray diffraction analysis (XRD); the main constituent of the graphite emulsion layer 130 is C, and the qualitative characterization manner of C is also various, such as a carbon-oxygen analyzer, etc., and the qualitative characterization method of oxide and C is available in the art and will not be described herein again.
The weight ratio of the composite layer in the text is tested by an alkaline cooking weight loss method: heating KOH with the concentration of 10% (based on the observation of bubbling), putting 1-3 g of 100 raw materials of the tungsten alloy wire into the solution, heating for 10min and continuously stirring, then fishing out the tungsten alloy wire 100, ultrasonically vibrating and cleaning for 5min by using alcohol, drying in the air, weighing, and detecting the weight loss of the wire before and after alkaline boiling; the weight ratio of the composite layer is (100 weight of tungsten alloy wire before alkali cooking-100 weight of tungsten alloy wire after alkali cooking)/100 weight of tungsten alloy wire before alkali cooking multiplied by 100%;
the probability of breakage is expressed herein using the breakage rate, which is (the number of produced pieces in the process-the number of input pieces of raw material)/the number of input pieces of raw material × 100%. The size of the die loss is mainly judged by observing and measuring the size variation of the die hole, the die loss is generally measured by the number of meters of wires produced when a single die is enlarged to a certain size, and the smaller the number of meters of wires is, the larger the die loss is.
As shown in fig. 4, D represents the wire diameter of the tungsten alloy wire, i.e., the diameter thereof, H1 represents the thickness of the composite layer, H3 represents the thickness of the oxide layer 120, and H2 represents the thickness of the graphite emulsion layer 130, where the thickness ratio of the oxide layer 120 to the composite layer is H2/H1 × 100%, and the thickness ratio of the graphite emulsion layer 130 to the composite layer is H3/H1 × 100%; the expression "to" is used herein to indicate a range of values, and the expression of the range includes two endpoints.
It should be noted that the core 110 is made of a metal wire made of tungsten or a tungsten alloy, and the specific selection of the core 110 can be made from the existing tungsten or tungsten alloy material.
The present invention also provides a preferred embodiment of the core 110 material, which is a metallic material composed of an alloy of tungsten and a rare earth oxide. The metal material formed by the alloy of tungsten and rare earth oxide specifically comprises the following components:
the content of tungsten is more than 90 wt%, and the content of rare earth oxide is more than 0.1 wt%; for example, the content of tungsten may be 95 wt% or more; preferably, the content of tungsten is 97.0 wt% to 99.9 wt%, such as 97.5 wt%, 98 wt%, 98.5 wt%, 99 wt%, 99.5 wt%, etc.;
for another example, the lanthanum oxide may be contained in an amount of 0.1 to 2 wt%, or 0.1 to 1 wt%, or 0.3 to 0.8 wt%, or of course, 0.1 wt%, 0.3 wt%, 0.5 wt%, 0.8 wt%, 1 wt%, 1.5 wt%, 2 wt%, or the like, and the lanthanum oxide is preferably lanthanum oxide (La) which is preferably used2O3) The performance of the core 110 material can be improved by increasing the oxide content of lanthanum, but the difficulty of refining the core 110 material can be greatly improved when the oxide content of lanthanum is greater than 2 wt%.
In addition, the rare earth oxide may be one or more;
for example, common rare earth oxides include dysprosium oxide (Dy)2O3) Erbium oxide (Er)2O3) Neodymium oxide (Nd)2O3) Yttrium oxide (Y)2O3) Europium oxide (Eu)2O3) Gadolinium oxide (Gd)2O3) Lanthanum oxide (La)2O3) Praseodymium oxide (Pr)6O11) Holmium oxide (Ho)2O3) Cerium oxide (CeO)2) Terbium oxide (Tb)4O7) Ytterbium oxide (Yb)2O3) Samarium oxide (Sm)2O3) Praseodymium neodymium oxide ((Pr + Nd)xOy) Thulium oxide (Tm)2O3)、Lutetium oxide (Lu)2O3) Scandium oxide (Sc)2O3) Promethium oxide (Pm)2O3) Etc.;
in practice, however, lanthanum oxide (La) alone may be contained2O3) Yttrium oxide (Y)2O3) Cerium oxide (CeO)2) Scandium oxide (Sc)2O3) One of the rare earth oxides may also contain lanthanum oxide (La)2O3) And other rare earth oxides, e.g. scandium (Sc) oxide2O3) Yttrium oxide (Y)2O3) Or other combinations of rare earth oxides, e.g. lanthanum oxide (La) together2O3) And cerium oxide (CeO)2) Lanthanum oxide (La)2O3) And yttrium oxide (Y)2O3) Lanthanum oxide (La)2O3) And scandium oxide (Sc)2O3) Cerium oxide (CeO)2) And yttrium oxide (Y)2O3) Etc.;
the rare earth oxide is mainly distributed at the grain boundary of a tungsten main phase (matrix phase), a small amount of rare earth oxide is distributed in matrix phase grains, and the rare earth oxide can be distributed in a linear or particle string shape.
The smaller the wire diameter of the material of the core 110, which is a tungsten alloy material composed of rare earth oxide and tungsten, the stronger the tensile strength, and the smaller the wire diameter of the material of the tungsten alloy material composed of rare earth oxide and tungsten, the wire diameter can be made smaller to 60 μm or less than that of a conventional pure tungsten wire, so that the tungsten alloy wire 100 having a small wire diameter and high tensile strength can be obtained by using the tungsten alloy material composed of rare earth oxide and tungsten, and is suitable for use as a saw wire, a cable, or the like.
In addition, the rare earth oxide may also be a rare earth-metal composite oxide such as YSZ, LSCO, or the like;
moreover, the tungsten alloy may contain trace amounts of carbides including TiC and ZrC, other rare elements including Re and the like, or metal and nonmetal elements including C and the like, including potassium, rhenium, molybdenum, iron, cobalt and the like; the content of K is less than 80ppm, and the addition of a proper amount of K can improve the high-temperature performance of the material, but the processing performance is influenced by over high content of K, so that cracks and broken filaments are caused;
further, the tungsten alloy wire 100 with different wire diameter specifications is prepared by wire drawing the tungsten alloy material composed of rare earth oxide and tungsten obtained in the above preferred embodiment, i.e. the core 110 material, by the above preparation method of the tungsten alloy wire 100, and the tungsten alloy wire 100 is tested for tensile strength, proof stress, and push-pull toughness by the following methods:
the tensile strength test method comprises the following steps: clamping a tungsten alloy wire rod 100 with the length of 200mm by using a standard tensile machine, and carrying out constant-speed loading on one end of the tungsten alloy wire rod to obtain tensile strength data and elastic ultimate strength;
the tensile strength is calculated by the following formula (1):
σ＝F/S……(1)
wherein F is the breaking force, N; s is the original sectional area, mm;
the push-pull toughness testing method comprises the following steps: the tungsten alloy wire 100 is wound around a straightened core wire 340 (the core wire can be the tungsten alloy wire 100 with the diameter of more than 60 mu m) for one circle, then the sample disc 310 applies reverse force (the weight 330 is added to be more than 8 g), and the high-speed wire winding is carried out by controlling the wire winding disc 320 through a motor. The tungsten alloy wire 100 winds around the core wire 340 to move, and the smaller the diameter of the core wire 340 is, the better the toughness is demonstrated by the tungsten alloy wire 100 passing through the continuous wire at high speed. 100 mu m tungsten alloy wires are preferred, and the reverse acting force is 50 g; 100 parts of 60-micron tungsten alloy wire, and 50g of reverse acting force; 100 parts of 40-micron tungsten alloy wire, and 12g of reverse acting force; 100 parts of 25 mu m tungsten alloy wire, and 8g of reverse acting force; the push-pull detection device is shown in figure 5.
The tensile strength of the tungsten alloy wire 100, i.e., the tensile strength, is 2800MPa or more. For example, the tensile strength of the tungsten alloy wire 100 may be 3200MPa or more, 3800MPa or more, 4200MPa, 4800MPa or 5000MPa or more;
the proof stress of the tungsten alloy wire 100 is 2500MPa or more. For example, the proof stress of the tungsten alloy wire 100 may be 2700MPa or more, 3000MPa or more, or 3200MPa or more;
the wire diameter of the tungsten alloy wire 100 is 400 μm or less. For example, the wire diameter of the tungsten alloy wire 100 is 400 μm, 350 μm, 300 μm, 250 μm, 200 μm, 150 μm, 100 μm, 80 μm, or even 60 μm, 40 μm, 25 μm, and 20 μm and 10 μm, etc.; the tungsten alloy composed of the rare earth oxide and tungsten, i.e., the core 110 material, may or may not be uniform completely, and may also contain differences in several percent effects, such as 1%, depending on the location; in particular, since the wire diameter of the tungsten alloy wire 100 may be 60 μm or less, the tungsten alloy wire 100 has flexibility and is easily bent sufficiently, and thus the tungsten alloy wire 100 can be easily wound;
thereby, the diameter of the push-pull core wire of the tungsten alloy wire 100 can be 350 μm or less. For example, 230 μm, 200 μm, 180 μm, 160 μm, 130 μm, etc., it can be seen that the tungsten alloy wire 100 also has excellent push-pull toughness;
specifically, the wire diameter of the tungsten alloy wire 100 is 200 μm to 400 μm, and the tensile strength of the tungsten alloy wire 100 is 2800MPa to 4000MPa, for example, the tensile strength reaches 3000MPa, also can reach 3500MPa, even reaches 4000 MPa;
the wire diameter of the tungsten alloy wire 100 is 100-200 mu m, the tensile strength of the tungsten alloy wire 100 is 3200-4800 MPa, for example, the tensile strength reaches 3400MPa, can also reach 4000MPa, can also reach 4500MPa, and even reaches 4800 MPa;
for example, the wire diameter of the tungsten alloy wire 100 is 100 μm or less; the tensile strength of the tungsten alloy wire 100 is more than 3800 MPa;
the wire diameter of the tungsten alloy wire 100 is 60 μm or less; the tensile strength of the tungsten alloy wire 100 is 4200MPa or more; the elastic limit strength of the tungsten alloy wire 100 is more than 2500MPa, and the diameter of a push-pull core wire of the tungsten alloy wire 100 is less than 350 μm, even less than 180 μm; the tungsten alloy is an alloy of tungsten and rare earth oxide;
the wire diameter of the tungsten alloy wire 100 is 40 μm or less; the tensile strength of the tungsten alloy wire 100 is 4800MPa or more; the elastic limit strength of the tungsten alloy wire 100 is more than 3000MPa, and the diameter of a push-pull core wire of the tungsten alloy wire 100 is less than 350 μm, even less than 200 μm;
the wire diameter of the tungsten alloy wire 100 is 25 μm or less; the tensile strength of the tungsten alloy wire 100 is more than 5000 MPa; the elastic limit strength of the tungsten alloy wire 100 is more than 3000MPa, and the diameter of a push-pull core wire of the tungsten alloy wire 100 is less than 350 μm, even less than 250 μm;
in the preferred embodiment of the utility model: the tungsten alloy wire containing tungsten and rare earth oxide has comprehensive performance superior to that of a rhenium tungsten alloy wire and a conventional pure tungsten wire in tensile strength and push-pull toughness, and is used as a core material, so that the performance of the tungsten alloy wire is improved.
It should also be noted that the selection of specific examples of the core 110 material from existing tungsten alloys containing tungsten and rare earth oxides, including but not limited to the preferred embodiments provided above, can be made by those skilled in the art based on the requirements of tensile strength, proof stress, push-pull core diameter, etc.
The present invention also provides a method for preparing the metal wire material composed of the alloy of tungsten and rare earth oxide, i.e., the core 110 material and the tungsten alloy wire 100 in the above preferred embodiment:
the preparation method of the tungsten alloy wire 100 comprises the steps of doping powder preparation, pressing, sintering, cogging, pressure processing and the like;
the doped powder preparation method comprises the following steps: doping, reducing and mixing powder; the doped powder preparation is divided into a solid-liquid mode, a liquid-liquid mode, a solid-solid mode and the like according to different process methods;
specifically, based on a solid-liquid mode, the doped powder preparation method comprises the following steps: solid-liquid doping, reducing and pulverizing;
the solid-liquid doping method comprises the following steps: doping a proper amount of soluble rare earth salt solution into tungsten powder, and after fully stirring, heating and drying in a staged manner to complete the solid-liquid doping step;
the staged heating and drying adopts a drying mode of firstly low temperature and then high temperature, namely, drying is carried out at the temperature lower than 100 ℃ to slowly separate out rare earth salt particles with more nucleation numbers, and then drying is carried out at the temperature higher than 100 ℃, so that the rare earth salt particles with more particle numbers cannot be combined and grown, and the particle size can be greatly refined;
the staged drying at least comprises 2 temperature stages, wherein the 2 temperature stages take 100 ℃ as a boundary line, are firstly heated and dried at 100 ℃, and are then heated and dried at more than 100 ℃; for example, the mixture is heated and dried for 2 to 6 hours at the temperature of between 60 and 80 ℃ and then heated and dried for 3 to 5 hours at the temperature of between 110 and 150 ℃;
it can be understood that, in the two temperature stages divided by the 100 ℃ as the boundary, the heating and drying of multiple temperature gradients or multiple temperature stages can be respectively performed, for example, the drying is performed first at 60 ℃ for 2h, then at 80 ℃ for 2h, and then the temperature is raised to 120 ℃ for drying; of course, the above-described embodiments represent only a few embodiments of the present invention, and it will be apparent to those skilled in the art that several temperature phase adjustments and changes may be made without departing from the inventive concept.
For example, a proper amount of rare earth nitrate solution is uniformly doped into the blue tungsten powder, and after the mixture is fully stirred, the mixture is firstly heated for 2 to 6 hours at the temperature of between 60 and 80 ℃ and then heated for 3 to 5 hours at the temperature of between 110 and 150 ℃, so that the doping and powder making steps are completed;
specifically, based on a liquid-liquid mode, the doped powder preparation method comprises the following steps: liquid-liquid doping, reducing and pulverizing;
the liquid-liquid doping method comprises the following steps: doping tungstic acid and/or tungstate solution with soluble rare earth salt solution for obtaining rare earth salt doped tungsten powder subsequently, namely completing the liquid-liquid doping step;
for example, a rare earth salt-doped blue tungsten powder is obtained by liquid-liquid doping using an ammonium metatungstate solution and a rare earth salt solution as raw materials;
specifically, based on the solid-solid mode, the doped powder preparation method comprises the following steps: solid-solid doping;
the solid-solid doping method comprises the following steps: adopting tungsten powder with Fisher particle size of 1.0-4.0 μm and rare earth oxide with particle size distribution D90<2.0 μm as raw materials, carrying out solid-solid doping mixing to obtain doped rare earth oxide tungsten powder, and completing the solid-solid doping step, namely completing the solid-solid doping powder preparation step;
further, in order to ensure the rare earth oxide particle size, the solid-solid doping step further comprises removing coarse particles by a water precipitation method to obtain rare earth oxide fine particles;
based on the characteristics of fast precipitation of coarse particles and slow precipitation of fine particles, the rare earth oxide with D90<2 mu m is obtained by 3-level precipitation with the precipitation time of 30-120 minutes;
in the case of the solid-liquid system and the liquid-liquid system, the reduction and pulverization steps in the above steps are preferably, but not limited to, the following embodiments:
reduction: the material prepared by doping in a solid-liquid and/or liquid-liquid mode is subjected to one-step reduction of doped powder into alloy powder in a four-temperature-zone reduction furnace;
milling: and mixing the reduced alloy powder, and placing the mixed alloy powder with the average Fisher grain size of 1.0-4.0 mu m into a powder mixer. Mixing the powder for 60-90 minutes at a rotating speed of 6-10 revolutions per minute to finish the step of doping and milling;
powder pressing: pressing powder formed by matching average Fisher granularity of 1.0-4.0 microns in an isostatic pressing mode into a pressed blank with the single weight of 1.5-5.0 kg under the pressure of 160-260 MPa, and pre-sintering the pressed blank in a hydrogen atmosphere, wherein the pre-sintering temperature is preferably 1200-1400 ℃, and the strength of the pressed blank is increased;
and (3) sintering: sintering is carried out, the sintering temperature is preferably 1800-2400 ℃, the sintering time is preferably 5-15 hours, and the density is 17.5-18.5 g/cm3Sintering the billet;
cogging: continuously rolling a sintered billet with the diameter of 15-25 mm into a tungsten alloy rod with the diameter of 8.0-12.0 mm by adopting a multi-roll mill at the heating temperature of 1600-1700 ℃, and preparing a metal material with a certain diameter specification, namely a core body 110 material, which is formed by an alloy of tungsten and rare earth oxide; when the multi-roller rolling mill is used, the ratio of the longitudinal length of the rare earth oxide particles in the rolled tungsten rod to the cross section particle size of the particles is more than 5;
pressure processing: (1) performing multi-pass rotary swaging on a metal material composed of tungsten or tungsten alloy, namely the core body 110 material; (2) and (2) repeating the core body 110 material obtained in the step (1) for a plurality of times to perform a wire drawing process: sequentially performing a wire unwinding step, a graphite emulsion coating step, a heating and drying step and a single-pass or multi-pass drawing step, and repeating the steps for multiple times until a wire rod with a certain wire diameter specification is obtained; (3) carrying out oxidation burning loss on the wire rod obtained after the wire drawing process treatment, namely carrying out oxidation burning loss on the wire rod before the final drawing step of preparing the expected wire diameter; (3) and performing a final wire drawing process: and (4) sequentially performing a graphite emulsion coating step, a heating and drying step and a multi-pass drawing step on the wire rod obtained in the step (3) to obtain the tungsten alloy wire rod 100 with the wire diameter specification required finally.
The utility model also provides the following examples and comparative examples:
example 1
In the embodiment of the present invention, a high-strength and high-toughness tungsten alloy wire 100 is prepared according to the present invention, and the material elements comprise: la2O31 wt% and W99 wt%.
The preparation steps are as follows:
step 1, doping: uniformly doping a proper amount of nitrate solution of lanthanum into blue tungsten powder, and drying the mixture in a mode of drying at a low temperature of 80 ℃ for 4 hours and then at a high temperature of 120 ℃ after fully stirring;
step 2, reduction: reducing the doped powder of the material obtained in the step 1 into alloy powder with proper granularity in a four-temperature-zone reducing furnace;
step 3, mixing powder: and (3) placing the materials obtained in the step (2) into a powder mixer according to different particle size compositions. Mixing the powder for 80 minutes at the rotating speed of 8 revolutions per minute;
step 4, powder pressing: pressing powder formed by matching different particle sizes into a pressed blank with the single weight of 3.0kg by adopting an isostatic pressing mode under the pressure of 200MPa, and pre-sintering the pressed blank at low temperature in a hydrogen atmosphere to increase the strength of the pressed blank;
and 5, high-temperature sintering: sintering at high temperature to obtain sintered billet with the density of 18.10g/cm 3;
step 6, cogging: continuously rolling the sintered billet with the diameter of 23.0mm into a tungsten alloy rod with the diameter of 8.0mm by adopting a multi-roll mill at the heating temperature of 1650 ℃, namely the core body 110 material;
step 7, (1) performing multi-pass rotary swaging on a metal material consisting of an alloy of tungsten and a rare earth oxide, namely the tungsten alloy rod prepared in the previous step to prepare a tungsten alloy rod with the thickness of 3.7 mm; (2) repeating the wire drawing process on the core body 110 material obtained in the step (1) for multiple times: sequentially performing a wire unwinding step, a graphite emulsion coating step, a heating and drying step and a drawing step, and repeating for multiple times until the wire diameter specification is thinned to 0.20 mm; before the wire diameter of the wire rod is 0.85 mm-4 mm, single-pass drawing is adopted in the drawing step, and after the wire diameter is less than 0.85mm, multi-pass drawing is adopted in the drawing step; (3) carrying out an oxidation burning process with the oxidation burning temperature of 1200 ℃; (4) a final wire drawing process: the wire rod with the wire diameter of 0.20mm is subjected to a wire unwinding step, a graphite emulsion coating step, a heating and drying step and a multi-pass drawing step in sequence to obtain the tungsten alloy wire rod 100 with the diameter of 100 microns.
Wherein the average particle size of the selected graphite emulsion particles is 1.53 mu m, and the specific gravity of the graphite emulsion is 1.035 +/-0.005 g/cm; the oxidation burning loss temperature of the wire rod with the wire diameter of 0.20mm before the finished product is 1200 ℃, namely the oxidation burning loss temperature in the final oxidation burning loss working procedure before the final drawing step for preparing the expected wire diameter is 1200 ℃; the reduction of the cross-sectional area of a single pass of the wire in the drawing step in the step (4) was 15%/pass.
The tungsten alloy wire 100 was tested to yield: tungsten alloy wire 100 having wire diameter of 100 μm: the thickness of the composite layer is 3 microns, the thickness of the oxide layer 120 is 1.95 microns, the thickness of the graphite emulsion layer 130 is 1.05 microns, and the alkali boiling weight loss is 2.3 percent, namely the weight of the composite layer accounts for 2.3 percent of the weight of the tungsten alloy wire rod, the production wire breakage rate is 6.3 percent, and the tensile strength is 3990 Mpa.
In addition, the tungsten alloy wire rods 100 with wire diameters of 60 μm, 40 μm and 25 μm were further manufactured according to the manufacturing method of the step 7, wherein the tungsten alloy wire rods 100 with wire diameters of 60 μm, 40 μm and 25 μm were manufactured, and the intermediate annealing temperature before finishing was 1350 ℃.
The tungsten alloy wire 100 described above was tested to yield: tungsten alloy wire 100 having wire diameter of 60 μm: the thickness of the composite layer is 1.04 mu m, the thickness of the oxide layer 120 is 0.68 mu m, the thickness of the graphite emulsion layer 130 is 0.36 mu m, the diameter of the push-pull core wire is 280 mu m, the elastic limit strength is 3025MPa, the tensile strength is 4560MPa, and the production filament breakage rate is low and the die loss is small;
Comparative example 1
In the embodiment of the present invention, a high-strength and high-toughness tungsten alloy wire 100 is prepared according to the present invention, and the material elements comprise: la2O3 was 1 wt%, and W was 99 wt%.
The preparation steps are as follows:
step 1, doping: uniformly doping a proper amount of nitrate solution of lanthanum into blue tungsten powder, and drying the mixture in a mode of drying at a low temperature of 80 ℃ for 4 hours and then at a high temperature of 120 ℃ after fully stirring;
step 2, reduction: reducing the doped powder of the material obtained in the step 1 into alloy powder with proper granularity in a four-temperature-zone reducing furnace;
step 3, mixing powder: and (3) placing the materials obtained in the step (2) into a powder mixer according to different particle size compositions. Mixing the powder for 80 minutes at the rotating speed of 8 revolutions per minute;
step 4, powder pressing: pressing powder formed by matching different particle sizes into a pressed blank with the single weight of 3.0kg by adopting an isostatic pressing mode under the pressure of 200MPa, and pre-sintering the pressed blank at low temperature in a hydrogen atmosphere to increase the strength of the pressed blank;
and 5, high-temperature sintering: sintering at high temperature to obtain sintered billet with the density of 18.10g/cm 3;
step 6, cogging: continuously rolling the sintered billet with the diameter of 23.0mm into a tungsten alloy rod with the diameter of 8.0mm by adopting a multi-roll mill at the heating temperature of 1650 ℃;
step 7, (1) the metal material formed by the alloy of tungsten and rare earth oxide, namely the tungsten alloy rod prepared in the previous step, is subject to multi-pass rotary swaging to prepare a tungsten alloy rod with the thickness of 3.7mm, and (2) the wire drawing process is repeated for multiple times: sequentially performing a wire unwinding step, a graphite emulsion coating step, a heating and drying step and a drawing step, and repeating for multiple times until the wire diameter specification is thinned to 0.20 mm; before the wire diameter of the wire rod is 0.85 mm-4 mm, single-pass drawing is adopted in the drawing step, and after the wire diameter is less than 0.85mm, multi-pass drawing is adopted in the drawing step; (3) the oxidation burning loss process is not carried out; (4) a final wire drawing process: then, the wire rod with the wire diameter of 0.20mm is subjected to a wire unwinding step, a graphite emulsion coating step, a heating and drying step and a multi-pass drawing step in sequence to obtain a tungsten alloy wire rod 100 with the diameter of 100 microns;
wherein the average particle size of the selected graphite emulsion particles is 3.5 mu m, and the specific gravity of the graphite emulsion is 1.01 +/-0.005 g/cm; the wire rod with the wire diameter of 0.2mm before the finished product is not subjected to the oxidation burning loss process; the reduction of the cross-sectional area of a single pass of the wire in the drawing step in the step (4) was 5%/pass.
The tungsten alloy wire 100 was tested to yield: the tungsten alloy wire 100 with the wire diameter of 100 mu m has the composite layer thickness of 1.5 mu m and the soda boiling weight loss of 0.5 percent, namely the weight ratio of the composite layer is 0.5 percent, wherein the thickness ratio of the oxide layer 120 to the composite layer is 86 percent, the thickness of the oxide layer 120 is 1.29 mu m, the thickness ratio of the graphite emulsion layer 130 to the composite layer is 14 percent, the thickness of the graphite emulsion layer 130 is 0.22 mu m, the wire breakage rate in production is 67.3 percent, and the die loss is observed to be large.
In addition, according to the above-mentioned manufacturing method of step 7, the tungsten alloy wire 100 having the wire diameters of 60 μm, 40 μm, and 25 μm is further manufactured, and since the wire breakage rate is as high as 67.3% in the process of reducing the wire diameter of the tungsten alloy wire 100 having the wire diameter of 100 μm, it is more difficult to further refine the wire diameter, and it is difficult to mass-produce the tungsten alloy wire 100 having the small wire diameter (specifically, the wire diameter is smaller than 100 μm, for example, 60 μm or smaller, 40 μm or smaller, and 25 μm or smaller) and having the properties such as high strength and high toughness.
The performance results of the comparative examples and examples are shown in table 1 below:
TABLE 1
Although terms such as core, composite layer, oxide layer, graphite emulsion layer, etc. are used more often herein, the possibility of using other terms is not excluded. These terms are used merely to more conveniently describe and explain the nature of the present invention; they are to be construed as being without limitation to any additional limitations that may be imposed by the spirit of the present invention.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the utility model has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A tungsten alloy wire characterized by: the core body and the composite layer coated on the surface of the core body are sequentially arranged from inside to outside;
the wire diameter of the tungsten alloy wire is 100 mu m or less;
the core body is a tungsten wire or a tungsten alloy wire;
the composite layer sequentially comprises an oxide layer and a graphite emulsion layer from inside to outside; the thickness of the composite layer is 0.2-5 microns, the thickness ratio of the oxide layer to the composite layer is 55-75%, and the thickness ratio of the graphite emulsion layer to the composite layer is 25-45%.
2. The tungsten alloy wire of claim 1, wherein: the core body is a rare earth tungsten alloy wire, the wire diameter of the tungsten alloy wire is 100 mu m or less, and the tensile strength of the tungsten alloy wire is more than 3800 MPa.
3. The tungsten alloy wire according to any one of claims 1 or 2, wherein: the wire diameter of the tungsten alloy wire is 60-100 mu m, and the thickness of the composite layer is 0.45-5 mu m.
4. The tungsten alloy wire of claim 1, wherein: the core body is a rare earth tungsten alloy wire, the wire diameter of the tungsten alloy wire is 60 mu m or less, the diameter of the push-pull core wire is 350 mu m or less, the proof stress is 2500MPa or more, and the tensile strength is 4200MPa or more.
5. The tungsten alloy wire according to any one of claims 1 or 4, wherein: the wire diameter of the tungsten alloy wire is 40-60 mu m, and the thickness of the composite layer is 0.25-2.5 mu m.
6. The tungsten alloy wire of claim 1, wherein: the core body is a rare earth tungsten alloy wire, the wire diameter of the tungsten alloy wire is less than 40 mu m, the tensile strength is more than 4800MPa, and the elastic limit strength is more than 3000 MPa.
7. The tungsten alloy wire according to any one of claims 1 or 6, wherein: the wire diameter of the tungsten alloy wire is 25-40 μm, and the thickness of the composite layer is 0.25-2.0 μm.
8. The tungsten alloy wire of claim 1, wherein: the core body is a rare earth tungsten alloy wire, the wire diameter of the tungsten alloy wire is 25 mu m or less, the tensile strength is more than 5000MPa, and the elastic limit strength is more than 3000 MPa.
9. The tungsten alloy wire according to any one of claims 1 or 8, wherein: the thickness of the composite layer is 0.2-1.25 μm.
10. The tungsten alloy wire of claim 1, wherein: the weight ratio of the composite layer to the tungsten alloy wire is 0.5-3.5%.
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| CN117778698A (en) * | 2023-12-14 | 2024-03-29 | 佛山朕华照明材料有限公司 | Metal wire processing system and processing method thereof |
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| WO2023153089A1 (en) * | 2022-02-10 | 2023-08-17 | パナソニックＩｐマネジメント株式会社 | Tungsten wire and metal mesh |
| CN117778698A (en) * | 2023-12-14 | 2024-03-29 | 佛山朕华照明材料有限公司 | Metal wire processing system and processing method thereof |
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