CN103801858B - Spot-wedling electrode electric spark on surface deposition TiB2The deposition rod of-TiC coating - Google Patents
Spot-wedling electrode electric spark on surface deposition TiB2The deposition rod of-TiC coating Download PDFInfo
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- CN103801858B CN103801858B CN201310683068.XA CN201310683068A CN103801858B CN 103801858 B CN103801858 B CN 103801858B CN 201310683068 A CN201310683068 A CN 201310683068A CN 103801858 B CN103801858 B CN 103801858B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/226—Non-corrosive coatings; Primers applied before welding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/222—Non-consumable electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K2101/00—Articles made by soldering, welding or cutting
- B23K2101/006—Vehicles
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- Powder Metallurgy (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The spot-wedling electrode electric spark on surface deposition TiB of the present invention2The deposition rod of-TiC duplex heat treatment, containing 60 ~ 80% (Ti+B4C+C) (wherein Ti powder occupies 74.8%, B to powder4C powder occupies 18.5%, C powder and occupies 6.7%) or containing 60 ~ 80% (TiB2+ TiC) powder (wherein TiB2Powder occupies (30-60) %, TiC powder and occupies (40-70) %), the Ni powder of (18 ~ 35) %, the Mo powder of (0.5 ~ 5) %, the W powder of (0.5-2) %. The TiB of the present invention2-TiC deposition rod obtains continuous, even, fine and close TiB by electric spark on surface deposition technology2-TiC duplex heat treatment, stable performance, can not only effectively improve life-span and the resistance to blocking of spot-wedling electrode, and technique of the present invention is simple, and its over-all properties is more superior, has stronger use value.
Description
Technical field
The present invention relates to the top coat processing technology of the processing technology of coating for metal surfaces, particularly spot-wedling electrode.
Background technology
In recent years along with ratio in ultimate production of the increase of auto output, particularly car continues to increase, the quality of automobile is had higher requirement by people. The visual appearance wherein how extending its service life and keep good is an important indicator, and the solidity to corrosion of automobile is the important factor affecting automotive service life. Based on above-mentioned requirements, traditional cold-rolled steel sheet can not meet the demand of this respect. Steel plate galvanized has excellent Anticorrosive Character, and thus application in fields such as automobile, household electrical appliances, buildings is more and more extensive, especially replaces cold-rolled steel sheet in automobile industry and is widely used. In automobile production industry, the type of attachment of this type of steel plate is main mainly with resistance welding, according to statistics, on each coachbuilt body, about there are 4000��6000 resistance spot welding solder joints, such as, during Shanghai Volkswagen's Passat body in white assembles, total solder joint number of every car reaches 5892 points, and the mean lifetime of each spot-wedling electrode is about 500��2500 points. Spot-wedling electrode is running stores the most frequently used in automotive body welding, maximum electrode cap purchase costs is wherein used to be generally Renminbi 5��20 yuan/right, as changed weekly 2��3 to electrode cap by a soldering turret, within 1 year, need to more exchange treaties 100 right, estimate that annual electrode drops into current domestic production total vehicle and will reach more than one hundred million unit. Moreover, during due to spot welding zinc coated steel, the viscous deformation of electrode is very fast and the life-span is also shorter, causes needing frequently to be repaired by electrode and change, and then makes production efficiency decline and production cost increase.Therefore, it is to increase electrode life, being one of the important topic that automobile manufacturing field is badly in need of solving, raising point quality is ensured auto-body assembly quality, control car body error, reduces production cost by this, it is to increase working efficiency has great significance.
In pinpoint welding procedure, electrode head diameter is generally the increase with electrode duration of service and increases, current density decline when the increase of electrode head diameter can cause spot welding and make the spot size of formation reduce (or decrease in strength), thus cause the inefficacy of spot-wedling electrode. Due to the work characteristics of spot-wedling electrode, especially weld steel plate galvanized time, its inefficacys roughly has following several mode: viscous deformation, degrade, alloying, hole lose and self-healing, recrystallize, thermal fatigue etc. Generally speaking, above-mentioned seven kinds of inefficacy mechanisms are all cause by high moderate pressure combined action.
The factor in Influential cases welding electrode work-ing life comprises electrode materials, the geometrical shape of electrode, the surface appearance of electrode head, welding condition. What raising electrode life had potentiality to be exploited most is research spot-wedling electrode material (comprising development of new spot-wedling electrode alloy, spot-wedling electrode matrix material) and electrode head is carried out surface treatment, wherein to spot-wedling electrode surface treatment most potentiality to be exploited. The surface being subject to the mainly electrode head of power, heat and metallurgy action due to electrode in pinpoint welding procedure, the surface of electrode head ought to be that raising electrode life is most economical, the most effective approach. The main coating method of spot-wedling electrode surface treatment there are electric spark deposition and physical vapor deposition. Gobez deposited cobalt, tantalum, nickel, TiN and molybdenum respectively on the CrZrCu electrode of spot welding galvanized steel, and result shows that the wear resisting property that first three coating makes reduce and latter two coating makes electrode electrode life slightly increases. The Studdon of Wollongong university TiN coated electrode coated electrode spot welding Zn-Al Coated Steels, welding current is lower by 10��20% than the electric current not being coated with CrN electrode, electrode life is longer than the life-span not being coated with CrN electrode, the spot-wedling electrode surface life-span not but being coated with CrN electrode is relatively stable, in about �� 7% change, and the spot-wedling electrode surface life-span being coated with CrN electrode changes about �� 40%. The bigger reason that fluctuates is that CrN coating exists many defects. The patent that Canada HuysIndustriesLimited has just reports the technique of spot-wedling electrode electric spark on surface built-up welding TiC layer, this type of electrode is when micro welding Nickeled Steel Plate and nickel plate, reach the twice that be CuCrZr electrode its electrode life at 1200, the TiC coating that the major cause improving electrode life is surperficial hinders the local welding between electrode and nickel plating plate and decreases the viscous deformation of electrode, in addition, the TiC layer of electrode surface can also improve the anti-adhesive properties of electrode; This type of ball type electrode reaches more than 1000 points the electrode life when the zinc-plated automotive sheet of spot welding, is 2.5 times of CuCrZr electrode, it is provided that the major cause of electrode life is that TiC coating delays and prevents the diffusion of Zn, has delayed and the alloying of electrode matrix copper. TiB2Relative TiC, is that the aspects such as electric conductivity, fusing point, hardness are all better than TiC, is also desirable electrode surface coating material. In order to TiB can be obtained on spot-wedling electrode surface2Coating, this is done a lot of work by the people such as Luo Cheng. Found that, the TiB that pre-acquired is desirable2Coating, it is necessary at the first deposition one layer of transition layer of electrode surface, this makes the deposition techniques of electrode become complicated, and greatly reduces the efficiency of electrode deposition, is unfavorable for promoting the use of on a large scale. TiB2TiC diphase ceramic material has the features such as high-melting-point, high rigidity, high heat conduction, low-expansion coefficient, high-wearing feature and satisfactory electrical conductivity, and relative to single-phase TiB2, TiB2Wettability between TiC diphase ceramic material and spot-wedling electrode matrix is better, it is not necessary to middle layer can directly at spot-wedling electrode surface deposited metal.
Chinese patent CN200410060704.4 discloses deposition rod and its preparation method of a kind of spot-wedling electrode electric spark on surface deposition coating, and the main component of deposition rod is TiB in this patent2. Chinese patent CN101775513A discloses a kind of mechanical alloying and prepares TiB2The method of-TiC dispersed and strengthened copper-based composite material. The Chinese patent method CN01115197.8 of gradient cladding " the metallic surface deposition coating particularly " although also can obtain TiB2-TiC coating, it is adopt then to adopt spraying method to be fixed on workpiece surface to adopt plasma body scanning to obtain coating again containing Fe base or Co base or Ni based powders add pottery due to this patent, the electric conductivity that the method obtains coating cannot meet spot-wedling electrode surface conduction requirement, so the surface treatment of spot-wedling electrode can not be used for, and technique is much more complicated than the present invention. Patent " roller surface TiC/TiB2Based ceramic metal composite strengthening method (CN102628867A) although also can obtain TiB2-TiC coating, owing to this patent have employed at workpiece surface spraying or built-up welding nickel-base alloy, then at nickel-base alloy surface (40-50%TiB2, 30-40%TiC, 10-15%Mo, 0.5-1.5%Cr, surplus is Fe) and ceramic electrode adopts the mode of electrical spark deposition to obtain TiC/TiB2Layer, due in this coating containing Fe, the electric conductivity obtaining coating in this way also cannot meet spot-wedling electrode surface conduction and require so the surface treatment of spot-wedling electrode can not be used for, and technique is much more complicated than the present invention.
Summary of the invention
The present invention is directed to problems of the prior art, it is provided that a kind of cost is low, and good conductivity, thermal conductivity is good, good with matrix wettability, the coating material spot-wedling electrode electric spark on surface deposition TiB that fusing point is high2The deposition rod its preparation method of-TiC duplex heat treatment.
The spot-wedling electrode electric spark on surface deposition TiB that the present invention relates to2The deposition rod of-TiC coating, it is characterised in that: with granularity at 100��200 orders, purity is all greater than Ti powder, the B of 99%4C powder, C powder, Ni powder, Mo powder, W powder are raw material, with (the Ti+B of weight percent 60��80%4C+C) (wherein Ti powder occupies 74.8%, B to powder4C powder occupies 18.5%, C powder and occupies 6.7%) the Ni powder of 18��35%, the Mo powder of 0.5��5%, the W powder Homogeneous phase mixing of 0.5-2%;
Or with granularity at 100��200 orders, purity is all greater than the TiB of 99%2Powder, TiC powder, Ni powder, Mo powder, W powder are raw material, with (the TiB of weight percent 60��80%2+ TiC) powder (wherein TiB2Powder occupies (30-60) %, TiC powder and occupies (40-70%)), the Ni powder of 18��35%, the Mo powder of 0.5��5%, the W powder Homogeneous phase mixing of 0.5-2%;
Adopt mechanical alloying, the preparation of vacuum half sintering process.
Adopt Ti powder, B4Deposition rod prepared by the powder such as C powder, C powder, its TiB2-TiC duplex heat treatment original position in electrical spark deposition process produces, and its coating performance is than directly adopting TiB2The coating performance of deposition rod prepared by the powder such as powder+TiC powder to be got well.
Spot-wedling electrode electric spark on surface deposition TiB2The preparation method of the deposition rod of-TiC coating, it is characterised in that: with granularity at 100��200 orders, purity is all greater than Ti powder, the B of 99%4C powder, C powder, Ni powder, Mo powder, W powder are raw material, with (the Ti+B of weight percent 60��80%4C+C) (wherein Ti powder occupies 74.8%, B to powder4C powder occupies 18.5%, C powder and occupies 6.7%), the Ni powder of 18��35%, the Mo powder of 0.5��5%, the W powder Homogeneous phase mixing of 0.5-2%;
Or with granularity at 100��200 orders, purity is all greater than the TiB of 99%2Powder, TiC powder, Ni powder, Mo powder, W powder are raw material, with the TiB of weight percent 60��80%2Powder+TiC powder (wherein TiB2Powder occupies (30-60) %, TiC powder and occupies (40-70%)), the Ni powder of 18��35%, the Mo powder of 0.5��5%, the W powder Homogeneous phase mixing of 0.5-2%;
It is that the steel ball of 10:1��50:1 and mixed powder put into ball grinder in the glove box of full argon gas ratio of grinding media to material, makes ball material mixture account for the 50��75% of spherical tank cavity volume; At room temperature carry out high-energy ball milling 24��48 hours with the rotating speed of 300��500 revs/min; Then above-mentioned mixed powder good for ball milling is added gross weight 2��10% viscose glue be pressed into required bar, bar sinters in vacuum oven under argon atmosphere at temperature range 900 DEG C��1150 DEG C becomes a useful person, and prepares and can meet deposition TiB2The deposition rod that-TiC needs.
The present invention adopts mechanical alloying, vacuum half sintering process to prepare electrical spark deposition TiB2-TiC duplex heat treatment deposition rod, has that technique is simple, production cost is low; Moreover, prepared TiB2-TiC deposition rod, compensate for TiC single-phase deposition rod specific conductivity low, TiB2The problems such as single-phase deposition rod is poor with spot-wedling electrode matrix wettability, and multilayer deposition techniques is complicated.
Below by the experimental data of example, TiB of the present invention is graphically described2The TiB that-TiC complex phase deposition rod obtains at spot-wedling electrode surface employing electrical spark deposition techniques2The performance of-TiC coating, and with traditional TiB2, TiC single-phase deposition rod adopt the TiB that electrical spark deposition techniques obtains on spot-wedling electrode surface2, TiC coating performance compare.
Table 1 is 6 kinds of TiB2-TiC deposition rod and single-phase TiC, TiB2The one-tenth submeter of deposition rod, table forms and is all weight percentage, table 1 gives different deposition rod simultaneously, at same electrical spark deposition techniques (voltage 24V, electrical capacity 30000 �� F, matrix rotating speed 1200r/min, vibrational frequency 50Hz and deposition time 120s) under the relevant information of coated electrode that obtains. As can be seen from Table 1, the coated electrode that present example 1��6 obtains, coating continuity is TiB relatively2Single-phase deposition rod is strong, and the coated electrode obtained does not have the phenomenon that obvious matrix exposes; Compared with the coated electrode that deposition single-phase with TiC rod obtains, the specific conductivity of coated electrode is higher.
Table 1
Table 2 is present example 1��6 and single-phase TiB2, TiC deposition rod adopt the coated electrode that obtains of electrical spark deposition techniques to be compare in life-span during 0.8mm steel plate galvanized at spot welding thickness on spot-wedling electrode surface, as can be seen from the table, the TiB obtained in electrode surface deposition with present example 1��62The life-span of-TiC duplex heat treatment and single-phase TiB2, the life-span height of TiB, TiC coating that obtains in electrode surface deposition of TiC deposition rod, be applicable to the connection of machinery industry spot welding zinc coated steel.
Table 2
| Example | Spot welding thickness is the mean lifetime during steel plate galvanized of 0.8mm |
| TiB2 | 1500 |
| TiC | 1000 |
| Embodiment 1 | 2050 |
| Embodiment 2 | 2000 |
| Embodiment 3 | 2100 |
| Embodiment 4 | 2050 |
| Embodiment 5 | 1950 |
| Embodiment 6 | 1900 |
Accompanying drawing explanation
Fig. 1 is the XRD of coating after deposition rod, electrical spark deposition after powder after present example 1 deposition baseball mill, half sintering. Fig. 2 uses present example 1TiB2-TiC deposition rod crosses, at spot-wedling electrode surface copper, the TiB that electrical spark deposition techniques obtains2The metallograph of-TiC duplex heat treatment and TiB2The outward appearance picture of-TiC duplex heat treatment electrode.
Embodiment
Example 1: by 72 grams of (Ti+B4C+C) (wherein Ti powder occupies 74.8%, B to powder4C powder occupies 18.5%; C powder occupies 6.7%); the Ni powder of 25 grams; the Mo powder of 2 grams; after the W powder Homogeneous phase mixing of 1 gram in ratio of grinding media to material be in the full argon balloon grinding jar of 35:1 at room temperature with the rotating speed of 400 revs/min under ball milling 30 hours; the viscose glue adding 5 by above-mentioned mixed powder good for ball milling gram is pressed into required bar, bar in vacuum sintering furnace, in argon atmosphere at 900 DEG C sintering become a useful person after for spot-wedling electrode electric spark on surface deposition.
Example 2: by 74 grams of (Ti+B4C+C) (wherein Ti powder occupies 74.8%, B to powder4C powder occupies 18.5%; C powder occupies 6.7%); 22 grams of Ni powder; 3 grams of Mo powder; after 1 gram of W powder, Homogeneous phase mixing in ratio of grinding media to material be in the full argon balloon grinding jar of 30:1 at room temperature with the rotating speed of 400 revs/min under ball milling 33 hours; the viscose glue adding 5 by above-mentioned mixed powder good for ball milling gram is pressed into required bar, bar in vacuum sintering furnace, in argon atmosphere at 950 DEG C sintering become a useful person after for spot-wedling electrode electric spark on surface deposition.
Example 3: by 76 grams of (Ti+B4C+C) (wherein Ti powder occupies 74.8%, B to powder4C powder occupies 18.5%; C powder occupies 6.7%); 21 grams of Ni powder; 2 grams of Mo powder; after 1 gram of W powder, Homogeneous phase mixing in ratio of grinding media to material be in the full argon balloon grinding jar of 35:1 at room temperature with the rotating speed of 400 revs/min under ball milling 36 hours; the viscose glue adding 5 by above-mentioned mixed powder good for ball milling gram is pressed into required bar, bar in vacuum sintering furnace, in argon atmosphere at 1000 DEG C sintering become a useful person after for spot-wedling electrode electric spark on surface deposition.
Example 4: by 75 grams of (Ti+B4C+C) (wherein Ti powder occupies 74.8%, B to powder4C powder occupies 18.5%; C powder occupies 6.7%); 21 grams of Ni powder; 3 grams of Mo powder; after 1 gram of W powder, Homogeneous phase mixing in ratio of grinding media to material be in the full argon balloon grinding jar of 35:1 at room temperature with the rotating speed of 400 revs/min under ball milling 39 hours; the viscose glue adding 5 by above-mentioned mixed powder good for ball milling gram is pressed into required bar, bar in vacuum sintering furnace, in argon atmosphere at 1050 DEG C sintering become a useful person after for spot-wedling electrode electric spark on surface deposition.
Example 5: by 33.5 grams of TiB2Powder, 38.5 grams of TiC powder; 25 grams of Ni powder; 2 grams of Mo powder; after 1 gram of W powder, Homogeneous phase mixing in ratio of grinding media to material be in the full argon balloon grinding jar of 40:1 at room temperature with the rotating speed of 400 revs/min under ball milling 40 hours; the viscose glue adding 8 by above-mentioned mixed powder good for ball milling gram is pressed into required bar; bar, in vacuum sintering furnace, sinters after becoming a useful person for spot-wedling electrode electric spark on surface deposition in argon atmosphere at 1050 DEG C.
Example 6: by 35 grams of TiB2Powder, 39 grams of TiC powder; 22 grams of Ni powder; 3 grams of Mo powder; after 1 gram of W powder, Homogeneous phase mixing in ratio of grinding media to material be in the full argon balloon grinding jar of 40:1 at room temperature with the rotating speed of 400 revs/min under ball milling 38 hours; the viscose glue adding 8 by above-mentioned mixed powder good for ball milling gram is pressed into required bar; bar, in vacuum sintering furnace, sinters after becoming a useful person for spot-wedling electrode electric spark on surface deposition in argon atmosphere at 1050 DEG C.
As shown in drawings: Fig. 1 is the XRD of coating after deposition rod, electrical spark deposition after powder after present example 1 deposition baseball mill, half sintering. Fig. 2 uses present example 1TiB2-TiC deposition rod crosses, at spot-wedling electrode surface copper, the TiB that electrical spark deposition techniques obtains2The metallograph of-TiC duplex heat treatment and TiB2The outward appearance picture of-TiC duplex heat treatment electrode.
Claims (1)
1. spot-wedling electrode electric spark on surface deposition TiB2The deposition rod of-TiC coating, it is characterised in that: with granularity at 100 ~ 200 orders, purity is all greater than Ti powder, the B of 99%4C powder, C powder, Ni powder, Mo powder, W powder are raw material, with the Ti+B of weight percent 60 ~ 80%4C+C powder, wherein Ti powder occupies 74.8%, B4C powder occupies 18.5%, C powder and occupies 6.7%, the Ni powder of 18 ~ 35%, the Mo powder of 0.5 ~ 5%, the W powder Homogeneous phase mixing of 0.5-2%;
Or with granularity at 100 ~ 200 orders, purity is all greater than the TiB of 99%2Powder, TiC powder, Ni powder, Mo powder, W powder are raw material, with the TiB of weight percent 60 ~ 80%2Powder+TiC powder, wherein TiB2Powder occupies 30-60%, and TiC powder occupies 40-70%, the Ni powder of 18 ~ 35%, the Mo powder of 0.5 ~ 5%, the W powder Homogeneous phase mixing of 0.5-2%;
It is that the steel ball of 10:1 ~ 50:1 and mixed powder put into ball grinder in the glove box of full argon gas ratio of grinding media to material, makes ball material mixture account for the 50 ~ 75% of spherical tank cavity volume; At room temperature carry out high-energy ball milling 24 ~ 48 hours with the rotating speed of 300 ~ 500 revs/min; Then above-mentioned mixed powder good for ball milling is added gross weight 2 ~ 10% viscose glue be pressed into required bar, bar sinters in vacuum oven under argon atmosphere at temperature range 900 DEG C ~ 1150 DEG C becomes a useful person, and prepares and can meet deposition TiB2The deposition rod that-TiC needs.
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| CN105171149B (en) * | 2015-10-28 | 2017-11-03 | 哈尔滨工业大学 | A kind of high energy micro arc NC postprocessing deposition process of titanium-fire-preventing coating |
| CN106271179B (en) * | 2016-08-31 | 2018-06-29 | 湖北工业大学 | A kind of ZrB2-CrB2Duplex heat treatment deposition stick and preparation method thereof |
| KR20190076784A (en) | 2017-12-22 | 2019-07-02 | 주식회사 포스코 | Manufacturing methods for the coating electrodes of the resistance welding |
| KR102306289B1 (en) | 2019-12-20 | 2021-10-01 | 주식회사 포스코 | Coated electode for resistance welding and manufacturing method thereof |
| CN114833338B (en) * | 2022-04-25 | 2023-06-13 | 西安交通大学 | Electroless plating NiMo modified TiB 2 TiC particle reinforced high manganese steel base composite material and preparation method thereof |
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| CN1586791A (en) * | 2004-08-08 | 2005-03-02 | 湖北汽车工业学院 | Coated stick of spot welding electrode surface electric spark coating layer and its preparing method |
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2013
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| DE4323149A1 (en) * | 1993-07-10 | 1995-01-12 | Audi Ag | Electrode for resistance welding |
| CN1586791A (en) * | 2004-08-08 | 2005-03-02 | 湖北汽车工业学院 | Coated stick of spot welding electrode surface electric spark coating layer and its preparing method |
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