CN113878037B - Titanium alloy and manufacturing method of titanium alloy watch appearance piece - Google Patents
Titanium alloy and manufacturing method of titanium alloy watch appearance piece Download PDFInfo
- Publication number
- CN113878037B CN113878037B CN202111180240.0A CN202111180240A CN113878037B CN 113878037 B CN113878037 B CN 113878037B CN 202111180240 A CN202111180240 A CN 202111180240A CN 113878037 B CN113878037 B CN 113878037B
- Authority
- CN
- China
- Prior art keywords
- titanium alloy
- blank
- manufacturing
- thermoforming
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 126
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- 238000003856 thermoforming Methods 0.000 claims abstract description 30
- 238000003754 machining Methods 0.000 claims abstract description 23
- 239000010936 titanium Substances 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 18
- 238000012545 processing Methods 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 238000005452 bending Methods 0.000 claims abstract description 11
- 238000004381 surface treatment Methods 0.000 claims abstract description 11
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims description 15
- 238000004321 preservation Methods 0.000 claims description 15
- 238000005498 polishing Methods 0.000 claims description 10
- 229910052582 BN Inorganic materials 0.000 claims description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000009434 installation Methods 0.000 claims description 5
- 230000001154 acute effect Effects 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000005488 sandblasting Methods 0.000 claims description 3
- 239000000956 alloy Substances 0.000 abstract description 9
- 238000007731 hot pressing Methods 0.000 description 29
- 230000007797 corrosion Effects 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000004576 sand Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 210000004243 sweat Anatomy 0.000 description 5
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012797 qualification Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- 201000004624 Dermatitis Diseases 0.000 description 1
- 230000000172 allergic effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D35/00—Combined processes according to or processes combined with methods covered by groups B21D1/00 - B21D31/00
- B21D35/002—Processes combined with methods covered by groups B21D1/00 - B21D31/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D22/00—Shaping without cutting, by stamping, spinning, or deep-drawing
- B21D22/02—Stamping using rigid devices or tools
- B21D22/022—Stamping using rigid devices or tools by heating the blank or stamping associated with heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D37/00—Tools as parts of machines covered by this subclass
- B21D37/16—Heating or cooling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D—WORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21D37/00—Tools as parts of machines covered by this subclass
- B21D37/18—Lubricating, e.g. lubricating tool and workpiece simultaneously
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
-
- G—PHYSICS
- G04—HOROLOGY
- G04B—MECHANICALLY-DRIVEN CLOCKS OR WATCHES; MECHANICAL PARTS OF CLOCKS OR WATCHES IN GENERAL; TIME PIECES USING THE POSITION OF THE SUN, MOON OR STARS
- G04B37/00—Cases
- G04B37/22—Materials or processes of manufacturing pocket watch or wrist watch cases
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Forging (AREA)
Abstract
The invention relates to the technical field of titanium alloy materials and watch part manufacturing, and in particular discloses a high-temperature-resistant and easy-to-process titanium alloy which comprises the following components in percentage by weight: al:3% -8%, si: 0-1%, V:0% -3%, zr:1% -5%, mo: 0-3%, sn: 0-5%, nd:0.5% -1.5%, other small amounts of impurity elements are not more than 2%, and the rest element is Ti. The manufacturing method of the titanium alloy watch appearance piece based on the titanium alloy material comprises the steps of processing a blank to form a blank A; installing a mould; heating the die and placing the blank A; primary thermoforming: after the blank A is kept warm for a preset time, pressurizing at a preset strain rate and maintaining pressure for a preset time to form a blank B; v-shaped grooves are formed on two folding surfaces of the large bending structure of the blank B to form a blank C; repeatedly thermoforming the blank C; repeatedly performing thermoforming for multiple times to form a blank D; cooling; machining; and (5) surface treatment.
Description
Technical Field
The invention relates to the technical field of titanium alloy materials and watch part manufacturing, in particular to a titanium alloy and a method for manufacturing a titanium alloy watch appearance part.
Background
In the watch industry, the watch appearance piece is usually processed by adopting 316L stainless steel as a raw material, and the stainless steel is high in density, heavy in weight and low in wearing comfort, and Ni element is often added into the stainless steel to improve corrosion resistance of the watch appearance piece, and the Ni element contacts with human skin, so that part of people can be allergic, and the watch appearance piece is not bio-friendly. The density of the titanium alloy material is low, and the mass of the titanium alloy material is only half of that of 316L steel under the same volume; corrosion resistance is also better than that of 316L steel, and the steel is not corroded after being subjected to artificial sweat and salt spray tests for a longer time; meanwhile, the titanium alloy also has biological friendliness, does not cause skin allergy and has good wearing comfort, so that the titanium alloy is widely used for manufacturing watch appearance parts. The traditional titanium alloy watch generally adopts a machining mode, and the strength and hardness of the titanium alloy are high, so that the machining is complex and difficult, particularly the machining difficulty of high-temperature titanium alloy is higher; in addition, in the machining process, the titanium alloy is easy to adhere to cutters and accumulate scraps, is difficult to dissipate heat, is easy to damage the cutters and even fires, greatly increases the machining cost and reduces the machining efficiency; in addition, most of titanium alloys have loose internal tissues, so that a plurality of sand holes exist on the surface of a finished product, and the aesthetic appearance is damaged.
In both patent numbers CN1083015C and TW397940B, a titanium alloy ornament is manufactured by hot-pressing a titanium alloy and then machining and surface treatment, so as to improve the surface quality thereof. However, because the high-temperature titanium alloy has high general strength, high hardness and relatively poor plasticity at high temperature, when the titanium alloy is processed by adopting the existing hot pressing technology, the deformation of the titanium alloy in one-time hot pressing forming is overlarge, so that the deformation resistance and the required pressure of the material are overlarge, the shearing stress generated under a large amount of compressive stress is overlarge, particularly, the stress is more concentrated at various positions with larger bending degree, the stress and the structure at the structure are often unstable, the surface of an extruded blank is extremely easy to wrinkle and even crack, the influence of the blank is difficult to eliminate after the polishing amount is large, the high requirement of the surface quality of the clock industry is not met, and meanwhile, the damage of hot pressing equipment is accelerated. In addition, in the above technical scheme, the hot pressing process parameters are not suitable for the high-temperature titanium alloy, specifically, the heating temperature in the TW397940B patent is 600-750 ℃, and compared with the high-temperature titanium alloy, the high-temperature titanium alloy has large deformation resistance due to the fact that the temperature is too low, and the bending surface of the pressed blank is easy to wrinkle and crack.
Therefore, the high-temperature titanium alloy can only be hot-pressed into a shape of a general part, and then more machining quantity is needed to reach the final size requirement, the machining difficulty still exists, and the efficiency is greatly reduced; in the hot pressing process, the titanium alloy blank is at a high temperature for too long, so that the titanium alloy blank is seriously oxidized, and an oxide layer is too thick; in addition, oxygen can diffuse into the matrix to form a brittle oxygen-enriched layer, thereby affecting the mechanical properties. Particularly for titanium alloy watch pieces, many parts have complex shapes, often have bending surface structures and large hole designs, the appearance ridge line is required to be lifted, and the structure and the requirement are difficult to finish by the existing hot press forming.
Disclosure of Invention
Accordingly, it is necessary to provide a titanium alloy which is resistant to high temperatures and is easy to process, and a method for manufacturing a titanium alloy watch exterior part, in order to solve the technical problem that hot press forming has a great influence on material properties.
A titanium alloy comprising the following components in weight percent: al:3% -8%, si: 0-1%, V:0% -3%, zr:1% -5%, mo: 0-3%, sn: 0-5%, nd:0.5% -1.5%, other small amounts of impurity elements are not more than 2%, and the rest element is Ti.
In one embodiment, the titanium alloy comprises the following components in weight percent: al:5% -7%, si:0 to 0.5 percent, V:0.5% -3%, zr:1% -3.5%, mo: 0-2%, sn: 0-4%, nd:0.5 to 1.2 percent, other small amounts of impurity elements are not more than 2 percent, and the rest element is Ti.
In one embodiment, the titanium alloy comprises the following components in weight percent: al:5% -6.5%, si:0 to 0.5 percent, V:0.8% -2.5%, zr:1.5 to 3.5 percent of Mo:0.5 to 2 percent of Sn:2% -4%, nd:0.8% -1.2%, other small amount of impurity elements are not more than 2%, and the rest element is Ti.
In one embodiment, the titanium alloy comprises the following components in weight percent: al:5.5 to 6.5 percent of Si:0.1 to 0.5 percent, V:0.8% -2.5%, zr:2.5 to 3.5 percent of Mo:0.5 to 1.5 percent of Sn: 3-4%, nd:0.8% -1.2%, other small amount of impurity elements are not more than 2%, and the rest element is Ti.
The invention also discloses a manufacturing method of the titanium alloy watch appearance piece, which adopts the titanium alloy and comprises the following steps:
s1, blank processing: cutting a titanium alloy blank into a required size, removing burrs, cleaning the surface of the blank, and spraying a high-temperature lubricant to form a blank A;
s2, die installation: cleaning a die, spraying high-temperature lubricant, and mounting the die on equipment;
s3, heating: heating the die to a specified forming temperature, preserving heat for a preset time, putting the blank A, and heating again at a preset heating rate and recovering to the specified forming temperature;
s4, primary thermoforming: after preserving heat for a preset time at the specified forming temperature in S3, pressurizing at a preset strain rate and maintaining pressure for a preset time to form a blank B;
s5, grooving: processing a preset number of V-shaped grooves on two folding surfaces of a large folding structure of the blank B to form a blank C;
s6, repeatedly thermoforming: continuously putting the blank C into a die, heating to a specified temperature, preserving heat for a preset time, pressurizing again, maintaining pressure for a preset time, and performing thermoforming on the blank C; repeatedly performing thermoforming for multiple times to form a blank D;
s7, cooling: opening the furnace to take the part after pressure relief, and cooling to normal temperature;
s8, machining: machining the cooled blank;
s9, surface treatment: and (3) polishing, drawing, sand blasting and coating surface treatment are carried out on the machined part according to the requirements, so that the part required by the final watch is formed.
In one embodiment, the high temperature lubricant sprayed in steps S1 and S2 is boron nitride.
In one embodiment, the heat preservation time in the step S3 is 20-30 min, and the heating rate is 750-800 ℃/min; in the step S4, the molding temperature is 700-800 ℃, the heat preservation time is 5-10 min, and the strain rate is 0.05-5S -1 The dwell time is 5-10 min.
In one embodiment, the included angle of the bending surface of the blank with the large bending structure of the blank B in the step S5 is 70-110 degrees; the dimension of the V-shaped groove is 0.5 mm-2 mm in width, 2 mm-8 mm in length and 0.5 mm-1.5 mm in depth, the bottom of the V-shaped groove is a round chamfer with the radius of 0.1 mm-1 mm, and the edge angles of two sides are acute angles; the number of the V-shaped grooves on each folding surface is 1-3.
In one embodiment, the number of times of repeated thermoforming in the step S6 is at least 2, the forming temperature of each thermoforming is 10-100 ℃ higher than that of the previous thermoforming, the heat preservation time is 10-15 min, and the pressure maintaining time is 10-15 min; the cooling method of step S7 is air cooling.
In one embodiment, the parts required for the watch in step S9 include a case, a bottom cover, a bezel, a wristband, a clasp, a handle or a dial.
By implementing the titanium alloy, the content of Al element is controlled to be 3-8%, so that the performances of oxidation resistance, hot workability, strength and the like of the titanium alloy are improved; nd accounting for 0.5% -1.5% is added, so that the wear resistance, strength and plasticity of the titanium alloy are improved; the Sn is increased by 0-5%, the compression ratio of the titanium alloy is increased, the volume fraction of the dendritic structure is increased due to the increase of the Nb and Sn, so that the plastic strain is further increased, the hot pressing difficulty is reduced, and the titanium alloy also has the advantages of light weight, biological friendliness, excellent corrosion resistance, good wearing comfort and the like commonly possessed by the titanium alloy.
By implementing the manufacturing method of the titanium alloy watch appearance piece, the deformation rate is controlled by adopting a plurality of thermoforming processes, so that the deformation resistance can be reduced, the dimensional accuracy of a formed part is improved, the loss rate of hot pressing equipment is reduced, the smooth proceeding of hot processing is facilitated, the blank after the plurality of hot pressing is close to net near forming, the later machining amount is greatly reduced, the loss rate of machining equipment and a cutter is reduced, the safety is improved, the qualification rate of finished products is improved, the use of titanium alloy raw materials is reduced, and the cost is saved; the V-shaped grooves are processed on the two folding surfaces of the large-bending-degree structure, when the metal is hot pressed, internal stress of the metal moves and gathers at sharp and defective positions, namely stress concentration effect, and by arranging the V-shaped grooves, the shearing stress and the compressive stress of the titanium alloy when the metal is hot pressed are concentrated at the bottom of the small groove and sharp edges on two sides, and the stress is greatly reduced in a deformation mode of the small groove, meanwhile, the deformation promotes the small groove to be closed, the small groove is thoroughly eliminated after the small groove is hot pressed for many times, and the surface quality of a blank is not influenced; the die is heated to the specified temperature, and then the titanium alloy blank is put into the die for continuous heating, so that the heating speed is high, the exposure time of the titanium alloy at high temperature is shorter, the oxide layer particles are smaller, the compactness is good, and the surface layer aesthetic property and the mechanical property are good; the surface of the titanium alloy can be densified by adopting a hot pressing mode, and the aesthetic property of a finished product is improved.
Drawings
FIG. 1 is a flow chart of a method of manufacturing a titanium alloy watch case of the present invention;
FIG. 2 is a schematic view of the structure of a V-shaped groove in the method for manufacturing a titanium alloy watch exterior part according to the present invention;
FIG. 3 is a schematic diagram of the metallographic structure of the titanium alloy of the present invention prior to hot pressing;
FIG. 4 is a schematic diagram of a metallographic structure of the titanium alloy of the present invention after hot pressing;
fig. 5 is a schematic structural view of a wristwatch case in embodiment 1 of the present invention;
fig. 6 is a schematic structural view of the bottom cover in embodiment 2 of the present invention.
Detailed Description
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to the appended drawings. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
The invention discloses a high-temperature-resistant and easy-to-process titanium alloy, which comprises the following components in percentage by weight: al:3% -8%, si: 0-1%, V:0% -3%, zr:1% -5%, mo: 0-3%, sn: 0-5%, nd:0.5% -1.5%, other small amounts of impurity elements are not more than 2%, and the rest element is Ti.
Further preferably, the titanium alloy comprises the following components in percentage by weight: al:5% -7%, si:0 to 0.5 percent, V:0.5% -3%, zr:1% -3.5%, mo: 0-2%, sn: 0-4%, nd:0.5 to 1.2 percent, other small amounts of impurity elements are not more than 2 percent, and the rest element is Ti.
Further, the titanium alloy comprises the following components in percentage by weight: al:5% -6.5%, si:0 to 0.5 percent, V:0.8% -2.5%, zr:1.5 to 3.5 percent of Mo:0.5 to 2 percent of Sn:2% -4%, nd:0.8% -1.2%, other small amount of impurity elements are not more than 2%, and the rest element is Ti.
In the preferred embodiment of the invention, the titanium alloy comprises the following components in percentage by weight: al:5.5 to 6.5 percent of Si:0.1 to 0.5 percent, V:0.8% -2.5%, zr:2.5 to 3.5 percent of Mo:0.5 to 1.5 percent of Sn: 3-4%, nd:0.8% -1.2%, other small amount of impurity elements are not more than 2%, and the rest element is Ti.
The titanium alloy has the advantages that the Al element content is controlled to be 3-8%, the Al element is increased, the oxidation resistance, the hot workability, the strength and other performances of the titanium alloy can be improved, but when the Al content exceeds 6%, the second phase Ti is formed 3 Al, when the content exceeds 7%, ti 3 The Al phase is mass-produced so that the strength of the titanium alloy is increased, but the plasticity and the stress corrosion resistance are drastically reduced, so that the Al element content needs to be controlled in order to ensure smooth hot forming and excellent comprehensive properties of the titanium alloy. In addition, the invention increases Nd accounting for 0.5 to 1.5 percent and Nd accounting for 0 to 5 percent% Sn. Because the solid solubility of Nd in the titanium matrix is very small, nd element is very easy to combine with O element in the high-temperature heat treatment process, and neodymium oxide particles are formed in situ, so that the effect of particle reinforcement is achieved, and the wear resistance, strength and plasticity of the titanium alloy are improved. The addition of a proper amount of Nb can also increase the compression ratio of the high-temperature titanium alloy, and the compression ratio is maximum when the Nb content is 1.0 percent. This is because Nb promotes the formation of β -Ti, which is a body-centered cubic structure, with relatively large internal slip, which is advantageous for plastic deformation of the material and increases the compression ratio, thereby making hot press processing easier. In addition, studies on titanium-based multicomponent alloys show that an increase in the amounts of Nb and Sn increases the volume fraction of the dendritic structure, further resulting in an increase in the amount of plastic strain, reducing the difficulty of hot pressing. The titanium alloy provided by the invention also has the advantages of light weight, biological friendliness, excellent corrosion resistance, good wearing comfort and the like which are commonly possessed by the titanium alloy.
Referring to fig. 1, the invention also discloses a method for manufacturing the appearance piece of the titanium alloy watch by adopting the titanium alloy material, which comprises the following steps:
s1, blank processing: cutting the titanium alloy blank into a required size, removing burrs, cleaning the surface of the blank, and spraying a high-temperature lubricant to form a blank A.
The titanium alloy blank in step S1 is a blank made of a titanium alloy of the aforementioned composition.
S2, die installation: the mold is cleaned, sprayed with a high temperature lubricant, and the mold is mounted to the apparatus.
The high-temperature lubricant sprayed in the steps S1 and S2 is boron nitride, the melting point of the boron nitride can reach 3000 ℃, and the high-temperature lubricant with good performance is obtained.
S3, heating: the mold is heated to the specified forming temperature, then kept warm for a predetermined time, then put into the blank a, heated again at a predetermined heating rate and returned to the specified forming temperature.
The heat preservation time in the step S3 is 20-30 min, and the heating rate is 750-800 ℃/min.
S4, primary thermoforming: after holding at the specified forming temperature for a predetermined time at S3, the blank B is formed by pressurizing at a predetermined strain rate and holding for a predetermined time.
In the step S4, the molding temperature is 700-800 ℃, the heat preservation time is 5-10 min, and the strain rate is 0.05-5S -1 The dwell time is 5-10 min, wherein the appointed forming temperature is the heat preservation temperature of the blank A in the primary hot forming operation. Because the high-temperature titanium alloy has higher hardness and strength, the deformation resistance of the hot pressing is larger, the heat preservation temperature is increased to 700-800 ℃ in the embodiment, and the deformation resistance is reduced by increasing the heat preservation temperature, so that the hot pressing processing is smoothly carried out. Meanwhile, boron nitride is added as a high-temperature lubricant, so that the demolding of the part is more convenient, the contact between the surface of the titanium alloy and oxygen in the air is reduced, and the oxidation degree of the surface layer of the titanium alloy is reduced.
S5, grooving: and processing a preset number of V-shaped grooves on two folding surfaces of the large folding structure of the blank B to form a blank C.
S5, forming an included angle of a bending surface of the blank with the large bending structure of the blank B into 70-110 degrees; the dimension of the V-shaped groove is 0.5 mm-2 mm in width, 2 mm-8 mm in length and 0.5 mm-1.5 mm in depth, the bottom of the V-shaped groove is a round chamfer with the radius of 0.1 mm-1 mm, and the edge angles of two sides are acute angles; the number of the V-shaped grooves on each folding surface is 1-3.
Specifically, referring to fig. 2, fig. 2 shows the structure of V-shaped grooves in the method, and the method innovatively adopts a groove cutting method to solve the problems of hot-pressing wrinkling and cracking of titanium alloy, namely, before hot pressing, a plurality of V-shaped grooves with smaller sizes are respectively formed in two folding surfaces of a structure with large bending degree. During hot pressing, internal stresses in the metal can move and accumulate at sharp, defective locations, i.e., stress concentrating effects. Therefore, during hot pressing, the shearing stress and the compressive stress in the titanium alloy are concentrated at the bottom of the small groove and the sharp edges at the two sides, the stress is greatly released and reduced in a small groove deformation mode, the small groove is closed by deformation, and the small groove is thoroughly eliminated after multiple hot pressing, so that the surface quality of a blank is not affected. It is noted that the concave small V-groove bottom cannot be too sharp to prevent the stress concentrating effect from being too great, causing the groove bottom to propagate into cracks.
S6, repeatedly thermoforming: continuously putting the blank C into a die, heating to a specified temperature, preserving heat for a preset time, pressurizing again, maintaining pressure for a preset time, and performing thermoforming on the blank C; and repeatedly performing thermoforming to form a blank D.
In the step S6, the repeated hot forming times are at least 2 times, the forming temperature of each hot forming is 10-100 ℃ higher than that of the former hot forming, the heat preservation time is 10-15 min, and the pressure maintaining time is 10-15 min.
Because most of high-temperature titanium alloy has high hardness, high strength and low plasticity, and the titanium alloy has a work hardening effect, the one-time hot forming resistance is high, the target size is difficult to reach, and a large amount of later processing is needed, so that the machining amount is increased, the processing is difficult, and the cutter is easy to accumulate heat to cause fire and damage equipment; and the deformation of the primary hot working is overlarge, and the compressive stress caused by overlarge shearing stress of the material, so that the surface of a finished product, particularly a large-bending-surface structure, can be wrinkled or even cracked in a large area, and the qualification rate of the finished product is low. The method adopts multiple times of thermoforming, controls the deformation rate, can reduce the deformation resistance, improves the dimensional accuracy of the formed part, reduces the loss rate of hot pressing equipment, and is favorable for smooth hot processing; in order to reduce the work hardening effect, the temperature or the heat preservation time of each hot forming is increased compared with that of the former hot forming so as to ensure that the process is carried out smoothly. In addition, the blank after multiple hot pressing is close to net near forming, the later machining amount is greatly reduced, the loss rate of machining equipment and cutters is reduced, the safety is improved, and the qualification rate of finished products is improved. The hot pressing process also reduces the use of titanium alloy raw materials and saves the cost.
S7, cooling: and opening the furnace to take the part after pressure relief, and cooling to normal temperature.
The cooling method in step S7 is air cooling, i.e., standing cooling in air.
S8, machining: and machining the cooled blank.
S9, surface treatment: and (3) polishing, drawing, sand blasting and coating surface treatment are carried out on the machined part according to the requirements, so that the part required by the final watch is formed.
The parts required for the watch in step S9 include the case, the bottom cover, the ring, the watch band, the clasp, the handle or the dial, in other words, the watch appearance part processed by the method includes the case, the bottom cover, the ring, the watch band, the clasp, the handle or the dial.
In the method, when the blank is heated, the die is heated to a specified temperature, and then the titanium alloy blank is put in for continuous heating. The method has the advantages that the blank heating speed is high, the exposure time of the titanium alloy at high temperature is shorter, the oxide layer particles are smaller, the compactness is good, and the surface layer attractiveness and the mechanical property are good; the thickness is thinner, less than 1 μm, and the oxidation degree is low.
In addition, the method adopts a hot pressing mode to process the titanium alloy, so that the surface of the titanium alloy is densified, and the aesthetic property of a finished product is improved. The metallographic structure of the titanium alloy raw material before hot pressing is shown in fig. 3, the surface of the titanium alloy raw material is loose and porous, and if polishing, sand drawing and other surface positions are directly carried out, a plurality of sand holes can appear, so that the attractiveness of the titanium alloy raw material is very affected. Referring to FIG. 4, after hot pressing, the titanium alloy sample is observed with 50 times magnification, the surface layer is compact and has no gaps within 500-700 μm, and after surface treatments such as polishing, sand drawing and the like, no sand holes are formed, so that the attractiveness is greatly improved. In addition, after the high-temperature titanium alloy is processed by a hot pressing process, the surface hardness is improved by 30-60 HV, and the surface wear resistance of the titanium alloy is improved.
The manufacturing method of the titanium alloy watch appearance piece is mainly aimed at high-temperature titanium alloy, is applicable to low-temperature titanium alloy, and is wide in application range.
The titanium alloy and the method of manufacturing the titanium alloy wristwatch appearance of the present invention will be further described below by means of the composition and processing methods of two specific examples of the wristwatch appearance.
Example 1
The titanium alloy in the embodiment comprises the following components in percentage by weight: 6.32% of Al, 0.12% of Si, 1.63% of V, 2.56% of Zr, 1.37% of Mo, 3.4% of Sn, 82.99% of Ti, 0.8% of Nb and 0.81% of other small impurity elements, and the titanium alloy consisting of the components is used as a raw material, so that the processed product has bright and beautiful surface appearance, excellent performance and high quality. With the titanium alloy material, the watch case shown in fig. 5 is manufactured by the following processing method of the appearance piece of the titanium alloy watch, and specifically includes the following steps:
s1, blank processing: cutting a titanium alloy blank into a required size, polishing with sand paper to remove burrs, cleaning the surface of the blank with alcohol, and spraying a high-temperature lubricant to form a blank A.
S2, die installation: the mold was cleaned and sprayed with a boron nitride lubricant, after which the mold was mounted to the apparatus.
S3, heating: the mold was heated to 700 ℃ and then incubated for 30min, then blank a was placed and reheated at 800 ℃/min back to 700 ℃.
S4, primary thermoforming: after 10min of heat preservation at 700 ℃, 2S is adopted -1 Pressurizing and maintaining the pressure for 5min to form a blank B.
S5, grooving: 2 small V-shaped grooves are respectively machined on the inner side of the surface lug of the blank B and the position close to the thin body of the surface lug, the small grooves are 1mm wide, 3mm long and 1mm deep, the bottoms are chamfer angles with the radius of 0.5mm, and edge angles of two sides of the small grooves are sharp to form the blank C.
S6, secondary thermoforming: heating to 750 ℃, preserving heat for 10min, pressurizing and maintaining the pressure for 10min to form a blank D.
S7, thermoforming for three times: continuously heating to 800 ℃, preserving heat for 15min, pressurizing and maintaining the pressure for 10min to form a blank E.
S8, cooling: and opening the furnace to take the part after pressure relief, and air-cooling to normal temperature.
S9, machining: the cooled watchcase blank E is simply machined to the final desired dimensions using CNC techniques.
S10, surface treatment: and (5) polishing and sanding the machined part according to the requirements.
The watchcase manufactured by the process has the advantages that the polished surface of the watchcase is bright and beautiful, the sand surface is uniformly stretched, no sand holes are visible to naked eyes, and the surface lugs and the thin parts are smooth and have no wrinkling or cracking. The hardness of the titanium alloy watch case was measured with a Vickers hardness tester to be about 340HV, which was increased by about 40HV as compared with the titanium alloy sample without hot pressing (298 HV). The watch case carries out 120-hour salt spray and 96-hour artificial sweat tests according to QB/T4775-2014 method for testing the corrosion resistance of the watch case body and the accessory artificial sweat, and the surface of the watch case has no corrosion phenomenon after the test. Assembled into a watch, the wearing feeling is light and comfortable.
Example 2
The titanium alloy in the embodiment comprises the following components in percentage by weight: 5.76% of Al, 0.35% of Si, 2.1% of V, 2.74% of Zr, 0.89% of Mo, 3.52% of Sn, 82.21% of Ti, 1.0% of Nb and 1.43% of other small amounts and impurity elements, and the titanium alloy consisting of the components is used as a raw material, so that the processed product has bright and beautiful surface appearance, excellent performance and high quality. With the titanium alloy material, the method for processing the appearance part of the titanium alloy watch in the embodiment is used for manufacturing the watch bottom cover shown in fig. 6, and specifically comprises the following steps:
s1, blank processing: cutting a titanium alloy blank into a required size, polishing with sand paper to remove burrs, cleaning the surface of the blank with alcohol, and spraying a high-temperature lubricant to form a blank A.
S2, die installation: the mold was cleaned and sprayed with a boron nitride lubricant, after which the mold was mounted to the apparatus.
S3, heating: the mold was heated to 750 ℃ and then incubated for 20min, then blank a was placed, and reheating was resumed at 750 ℃ at a rate of 750 ℃/min.
S4, primary thermoforming: after heat preservation at 750 ℃ for 5min, the mixture is treated by 1S -1 Pressurizing and maintaining the pressure for 10min to form a blank B.
S5, grooving: and 3 small V-shaped grooves are respectively machined on two sides of the vertical inner ring of the bottom cover, the small grooves are 0.5mm wide, 2mm long and 0.5mm deep, the bottoms are chamfer angles with the radius of 0.3mm, and the edges of the two sides of the small grooves are sharp, so that a blank C is formed.
S6, secondary thermoforming: continuously heating to 780 ℃, preserving heat for 10min, pressurizing and maintaining the pressure for 10min to form a blank D.
S7, thermoforming for three times: heating to 830 ℃, preserving heat for 15min, pressurizing and maintaining the pressure for 10min to form a blank E.
S8, four times of thermoforming: continuously heating to 930 ℃, preserving heat for 10min, pressurizing and maintaining the pressure for 15min to form a blank F.
S9, cooling: and opening the furnace to take the part after pressure relief, and air-cooling to normal temperature.
S10 machining: the cooled bottom cover blank E is simply machined to the final desired dimensions using CNC techniques.
S11, surface treatment: and (5) carrying out grinding and polishing treatment on the machined part according to the requirements.
The bottom cover manufactured by the process is bright and beautiful, has no sand holes visible to naked eyes, and has no wrinkling or cracking of the inner ring of the bottom cover. The hardness of the titanium alloy bottom cover was 373HV as measured by vickers hardness tester, and increased by about 30HV as compared with the titanium alloy sample block without hot pressing (346 HV). The watch case performs 120-hour salt spray and 120-hour artificial sweat test according to QB/T4775-2014 method for testing corrosion resistance of watch case and accessory artificial sweat, and the surface of the watch case has no corrosion phenomenon after test. Assembled into a watch, the wearing feeling is light and comfortable.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. The manufacturing method of the titanium alloy watch appearance piece is characterized by adopting a titanium alloy, wherein the titanium alloy comprises the following components in percentage by weight: al:3% -8%, si: 0-1%, V:0% -3%, zr:1% -5%, mo: 0-3%, sn: 0-5%, nd:0.5% -1.5%, other small amounts of impurity elements are not more than 2%, and the rest elements are Ti;
the method comprises the following steps:
s1, blank processing: cutting a titanium alloy blank into a required size, removing burrs, cleaning the surface of the blank, and spraying a high-temperature lubricant to form a blank A;
s2, die installation: cleaning a die, spraying high-temperature lubricant, and mounting the die on equipment;
s3, heating: heating the die to a specified forming temperature, preserving heat for a preset time, putting the blank A, and heating again at a preset heating rate and recovering to the specified forming temperature;
s4, primary thermoforming: after preserving heat for a preset time at the specified forming temperature in S3, pressurizing at a preset strain rate and maintaining pressure for a preset time to form a blank B;
s5, grooving: processing a preset number of V-shaped grooves on two folding surfaces of a large folding structure of the blank B to form a blank C;
s6, repeatedly thermoforming: continuously putting the blank C into a die, heating to a specified temperature, preserving heat for a preset time, pressurizing again, maintaining pressure for a preset time, and performing thermoforming on the blank C; repeatedly performing thermoforming for multiple times to form a blank D;
s7, cooling: opening the furnace to take the part after pressure relief, and cooling to normal temperature;
s8, machining: machining the cooled blank;
s9, surface treatment: and (3) polishing, drawing, sand blasting and coating surface treatment are carried out on the machined part according to the requirements, so that the part required by the final watch is formed.
2. The method for manufacturing a titanium alloy watch case according to claim 1, wherein the titanium alloy comprises the following components in percentage by weight: al:5% -7%, si: 0-0.5%, V:0.5% -3%, zr:1% -3.5%, mo: 0-2%, sn: 0-4%, nd:0.5% -1.2%, other small amounts of impurity elements are not more than 2%, and the rest element is Ti.
3. The method for manufacturing a titanium alloy watch case according to claim 2, wherein the titanium alloy comprises the following components in percentage by weight: al:5% -6.5%, si: 0-0.5%, V:0.8% -2.5%, zr:1.5% -3.5%, mo: 0.5-2%, sn:2% -4%, nd:0.8% -1.2%, other small amounts of impurity elements are not more than 2%, and the rest element is Ti.
4. The method for manufacturing a titanium alloy watch case according to claim 2, wherein the titanium alloy comprises the following components in percentage by weight: al:5.5% -6.5%, si:0.1 to 0.5%, V:0.8% -2.5%, zr:2.5% -3.5%, mo: 0.5-1.5%, sn: 3-4%, nd:0.8% -1.2%, other small amounts of impurity elements are not more than 2%, and the rest element is Ti.
5. The method of manufacturing a titanium alloy wristwatch appearance according to claim 1, wherein the high temperature lubricant sprayed in steps S1 and S2 is boron nitride.
6. The method for manufacturing the titanium alloy watch appearance piece according to claim 1, wherein the heat preservation time in the step S3 is 20-30 min, and the heating rate is 750-800 ℃/min; in the step S4, the molding temperature is 700-800 ℃, the heat preservation time is 5-10 min, and the strain rate is 0.05-5S -1 The pressure maintaining time is 5-10 min.
7. The manufacturing method of the titanium alloy watch appearance piece according to claim 1, wherein an included angle of a bending surface of a blank of the large bending structure of the blank B in the step S5 is 70-110 degrees; the size of the V-shaped groove is 0.5 mm-2 mm in width, 2 mm-8 mm in length and 0.5 mm-1.5 mm in depth, the bottom of the V-shaped groove is a round chamfer with the radius of 0.1 mm-1 mm, and the edge angles of the two sides are acute angles; the number of the V-shaped grooves on each folding surface is 1-3.
8. The method for manufacturing a titanium alloy watch exterior part according to claim 1, wherein in the step S6, the number of times of repeated thermoforming is at least 2, the forming temperature of each thermoforming is 10-100 ℃ higher than that of the previous thermoforming, the heat preservation time is 10-15 min, and the dwell time is 10-15 min; the cooling method of step S7 is air cooling.
9. The method of manufacturing a titanium alloy wristwatch exterior part according to claim 1, wherein the parts required for the wristwatch in step S9 include a case, a bottom cover, a bezel, a wristband, a clasp, a handle, or a dial.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111180240.0A CN113878037B (en) | 2021-10-11 | 2021-10-11 | Titanium alloy and manufacturing method of titanium alloy watch appearance piece |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111180240.0A CN113878037B (en) | 2021-10-11 | 2021-10-11 | Titanium alloy and manufacturing method of titanium alloy watch appearance piece |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113878037A CN113878037A (en) | 2022-01-04 |
| CN113878037B true CN113878037B (en) | 2023-11-03 |
Family
ID=79006022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111180240.0A Active CN113878037B (en) | 2021-10-11 | 2021-10-11 | Titanium alloy and manufacturing method of titanium alloy watch appearance piece |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113878037B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115401417A (en) * | 2022-09-15 | 2022-11-29 | 南通鑫威汽车配件制造有限公司 | Production process of automobile skylight mounting plate |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55147427A (en) * | 1979-05-08 | 1980-11-17 | Kawasaki Steel Corp | End plate forming method |
| CN102653046A (en) * | 2011-03-03 | 2012-09-05 | 赵凯志 | Method for manufacturing hub of high-performance cross-country recreational vehicle |
| CN104786014A (en) * | 2014-01-21 | 2015-07-22 | 无锡市前洲西塘锻压有限公司 | Manufacturing method for titanium composite plate plugs |
| CN105215160A (en) * | 2015-10-29 | 2016-01-06 | 武汉理工大学 | A kind of multistation Continuous Heat stamping line and method |
| CN107904440A (en) * | 2017-11-23 | 2018-04-13 | 北京工业大学 | A kind of high-temperature titanium alloy material and preparation method thereof |
| CN108188315A (en) * | 2017-12-07 | 2018-06-22 | 陕西宏远航空锻造有限责任公司 | A kind of forging method for improving the small forging macrostructure of titanium alloy |
| CN113355560A (en) * | 2021-08-10 | 2021-09-07 | 北京煜鼎增材制造研究院有限公司 | High-temperature titanium alloy and preparation method thereof |
-
2021
- 2021-10-11 CN CN202111180240.0A patent/CN113878037B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55147427A (en) * | 1979-05-08 | 1980-11-17 | Kawasaki Steel Corp | End plate forming method |
| CN102653046A (en) * | 2011-03-03 | 2012-09-05 | 赵凯志 | Method for manufacturing hub of high-performance cross-country recreational vehicle |
| CN104786014A (en) * | 2014-01-21 | 2015-07-22 | 无锡市前洲西塘锻压有限公司 | Manufacturing method for titanium composite plate plugs |
| CN105215160A (en) * | 2015-10-29 | 2016-01-06 | 武汉理工大学 | A kind of multistation Continuous Heat stamping line and method |
| CN107904440A (en) * | 2017-11-23 | 2018-04-13 | 北京工业大学 | A kind of high-temperature titanium alloy material and preparation method thereof |
| CN108188315A (en) * | 2017-12-07 | 2018-06-22 | 陕西宏远航空锻造有限责任公司 | A kind of forging method for improving the small forging macrostructure of titanium alloy |
| CN113355560A (en) * | 2021-08-10 | 2021-09-07 | 北京煜鼎增材制造研究院有限公司 | High-temperature titanium alloy and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113878037A (en) | 2022-01-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1083015C (en) | High-strength titanium alloy, product thereof, and method for producing the product | |
| JP4041774B2 (en) | Method for producing β-type titanium alloy material | |
| CN109468561B (en) | Preparation method of GH3625 alloy strip | |
| CN113878037B (en) | Titanium alloy and manufacturing method of titanium alloy watch appearance piece | |
| JP5829213B2 (en) | Stress relaxation heat treatment of titanium alloy parts | |
| JPH07150274A (en) | Titanium alloy and its production | |
| WO2002099151A3 (en) | Process to produce 6xxx alloys | |
| CN108866401A (en) | A kind of manufacturing method of the aluminium alloy strips of automobile decoration | |
| US20160153076A1 (en) | Hardened cobalt based alloy jewelry and related methods | |
| CA1108441A (en) | Fabricating process for high strength, low ductility nickel base alloys | |
| EP3475013B1 (en) | Methods of forming an oxide layer on a metal body | |
| JP3376240B2 (en) | High-strength titanium alloy, product thereof, and method of manufacturing the product | |
| US3537828A (en) | Composite stainless steel article | |
| US3035341A (en) | Manufacturing method for making molybdenum base alloy articles | |
| US20150107721A1 (en) | Methods of preparing a surface of a cast zirconium alloy substrate for oxidation | |
| CN109794556A (en) | A kind of bender lower die production method | |
| JP3653089B1 (en) | Silver alloy product and jewelry and method for producing silver alloy product | |
| CN111822535B (en) | Manufacturing method of lightweight metal belt | |
| CN110586826A (en) | Preparation method of aluminum alloy shell | |
| JP2912761B2 (en) | Manufacturing method of ferritic stainless steel | |
| JP2839605B2 (en) | Manufacturing method of titanium watch exterior parts | |
| JPH08319555A (en) | Treatment of iron-chrome-nickel-aluminum ferritic alloy | |
| JPS6362818A (en) | Production of external parts for timepiece | |
| JPS63216969A (en) | Working method | |
| DE1621290A1 (en) | Process for the production of smooth, flame-sprayed coatings from hard metal alloys |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |