CN113234981A - High-temperature-resistant high-thermal-expansion-coefficient hard alloy - Google Patents
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- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
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Abstract
The invention discloses a high temperature resistant and high thermal expansion coefficient hard alloy, which is prepared from nickel powder, chromium carbide powder, tungsten carbide powder and lead oxide powder. The weight ratio of the raw materials is as follows: the mass percentage of the nickel powder is 10-18%; the mass ratio of the chromium carbide powder is 25-40%; the mass percentage of the tungsten carbide powder is 35-55%; the mass percentage of the lead oxide powder is 2-10%. The preparation method comprises the following steps: taking raw materials, and additionally adding paraffin powder to form a mixture; grinding, drying, screening, pressing and semi-processing the mixture, and sintering the mixture at a temperature of 1280-1380 ℃ in an argon atmosphere at a pressure of 40-80 bar; and annealing and finishing the sintered mixture to obtain a finished product. The invention has the advantages that: the hard alloy has high hardness, and can achieve mirror surface appearance equivalent to that of the conventional hard alloy after being polished at normal temperature; the method has the advantages of convenient production, stable and controllable material quality and suitability for industrial production.
Description
Technical Field
The invention relates to the field of production and manufacturing of a mold material for hot bending of 3D curved glass, in particular to a high-temperature-resistant high-thermal-expansion-coefficient hard alloy.
Background
With the development of the mobile phone industry and the 5G technology, the frequency of electromagnetic wave radiation is higher and higher, which requires that the cover plate of the mobile phone is more and more prone to use a glass material that is easy to transmit electromagnetic radiation to achieve a good signal receiving effect. Meanwhile, in order to enable the mobile phone to have better holding feeling and attractive effect, the cover plate of the mobile phone made of the curved glass material is becoming a development trend of the industry, and the front surface and the back surface of part of high-end mobile phones are both provided with curved screens. At present, the hot bending of the curved glass of the mobile phone mainly adopts graphite which is high temperature resistant, good in oxidation resistance and easy to process as a mold, but the graphite has poor wear resistance, is easy to scratch and has short service life, and is influenced by the low thermal expansion coefficient of the graphite, and the graphite mold can only produce the hot bending glass with small curvature. Therefore, a mold material which is resistant to high temperature and oxidation and has a high thermal expansion coefficient is urgently needed in the field of curved glass hot bending.
A patent 3D glass hard alloy die and a manufacturing method thereof (CN 110878410A) provides a manufacturing method of a 3D glass hard alloy die, which comprises the steps of providing a hard alloy die blank; placing the hard alloy die blank into a reaction chamber and exhausting air in the reaction chamber; heating the reaction chamber, and reducing the oxide on the inner surface of the die cavity of the hard alloy die blank; introducing carbon-containing gas and halide gas of substances to be deposited, and reacting and depositing the carbon-containing gas and the halide gas on the inner surface of the blank die cavity of the hard alloy die to form a deposition layer so as to obtain the 3D glass hard alloy die, wherein the hard alloy matrix is one of WC-Co alloy, WC-TiC-TaC-Co alloy, tungsten carbide-based alloy and titanium carbide-based alloy, and the thermal expansion coefficient of the hard alloy matrix is concentrated in 4.5-7.4 multiplied by 10-6/° c, large curvature 3D glass hot bending is not suitable.
The patent (CN111118377A) provides a soaking plate material in the hot bending process of 3D curved glass, and a mold material which is not in direct contact with the glass.
Patent CN201710300221.4 discloses a preparation method of self-lubricating hard alloy, which uses graphene as one of the raw materials to obtain the effect of lubricating the surface of the hard alloy, and the raw material graphene has the characteristics of high price and difficult purchase, and is not beneficial to large-scale production.
Patent CN201811332483.X discloses a self-lubricating hard alloy wire drawing die and a preparation method thereof, wherein graphite, CaF2 and MgF2 are used as lubricating phases and added into a conventional tungsten carbide cobalt hard alloy matrix to prepare the self-lubricating hard alloy, the material adopts the conventional tungsten carbide cobalt hard alloy matrix, and the thermal expansion coefficient of the material is also concentrated at 4.5-7.4 multiplied by 10-6/° c, not suitable for large curvature 3D glass hot bending.
Disclosure of Invention
In order to solve the problems of difficult hot bending of large-curvature mobile phone glass and short service life of a graphite mold, the invention provides the hard alloy for hot bending of the 3D curved glass, which has good high-temperature resistance and oxidation resistance and reaches 9.5-11.0 multiplied by 10-6The thermal expansion coefficient and good high-temperature self-lubricating property of/° C are suitable for the thermal bending of 3D curved glass with large curvature at the temperature of 600-.
The technical scheme adopted by the invention is as follows: the high temperature resistant hard alloy with high heat expansion coefficient has material comprising nickel (Ni) powder of FSSS granularity 0.5-3.0 micron and chromium carbide (Cr) of FSSS granularity 0.5-3.0 micron3C2) The powder is tungsten carbide (WC) powder with the FSSS granularity of 1.0-6.0 and lead oxide (PbO) powder with the FSSS granularity of 1.0-5.0 mu m.
Further, the raw materials comprise the following components in percentage by mass:
the mass percentage of the nickel powder is 10-18%;
chromium carbide (Cr)3C2) The mass of the powder accounts for 25-40%;
the mass percentage of the tungsten carbide powder is 35-55%;
the mass percentage of the lead oxide (PbO) powder is 2-10%.
Further, the preparation method of the high-temperature-resistant high-thermal-expansion-coefficient hard alloy comprises the following steps: providing 10-20% by mass of nickel powder, 25-40% by mass of chromium carbide powder, 35-55% by mass of tungsten carbide powder, 2-10% by mass of lead oxide (PbO) powder and 3.5-4.5% by mass of paraffin powder in addition to form a mixture;
grinding the mixture;
drying the mixture;
sieving the mixture;
compressing the mixture;
semi-processing the mixture compact;
sintering the mixture in a dewaxing-sintering integrated low-pressure furnace at a temperature of 1280-1380 ℃ under a pressure of 40-80bar argon atmosphere;
and (5) annealing and fine processing the sintered mixture compact to obtain a finished product.
The invention has the advantages that: 1) has good high-temperature resistance and oxidation resistance, and the oxidation weight gain is only (6.5-10) mg-cm under the air environment of 900 DEG C-2·h-1Is obviously superior to the conventional WC-Co- (Ni) - (Cr)3C2) Oxidation weight gain (50-100) mg/cm of (VC) - (TaC) - (NbC) hard alloy-2·h-1(ii) a 2) Has a high value of 9.5 to 11.0 x 10-6The thermal expansion coefficient per DEG C is 5.0-7.5 x 10 higher than that of the conventional hard alloy-6The coefficient of thermal expansion of graphite is less than 3.0 × 10-6The temperature per DEG C is better, the method can be suitable for the hot bending of 3D curved glass with large curvature, and even suitable for the hot bending of glass with an angle of more than or equal to 180 degrees; 3) adding high-temperature self-lubricating component PbO and high-temperature reaction product PbWO of PbO4The lubricating effect is good, the 3D glass can be smoothly demoulded after being subjected to hot bending forming, and the scratch on the surface of the glass is small; 4) the hard alloy has high hardness, and can achieve mirror surface appearance equivalent to that of the conventional hard alloy after being polished at normal temperature; 5) the method has the advantages of convenient production, stable and controllable material quality and suitability for industrial production.
Drawings
FIG. 1 phase diagram of cemented carbide gold in example 1.
Figure 2 phase diagram of cemented carbide gold in example 2.
FIG. 3 phase diagram of cemented carbide gold in example 3.
Detailed Description
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 the described embodiments are only a part of the embodiments of the present invention, but not all of the embodiments. 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.
Example 1
A high-temp-resistant hard alloy with high thermal expansion coefficient is prepared from Ni powder (FSSS granularity 2.0 microns, 0.8 microns Cr)3C2Powder, WC powder with FSSS granularity of 4.0 μm, PbO powder with FSSS granularity of 3.0 μm, 15% of Ni and Cr3C232% by mass, 50% by mass of WC, 3% by mass of PbO and 3.6% by mass of an additional paraffin binder powder to form a mixture;
grinding the mixture;
drying the mixture;
sieving the mixture;
compressing the mixture;
semi-processing the mixture compact;
sintering the mixture in a dewaxing-sintering integrated low pressure furnace under argon atmosphere at a pressure of 50bar at a temperature of 1360 ℃;
and (5) annealing and fine processing the sintered mixture compact to obtain a finished product.
The hardness of the hard alloy is HRA89.6, a smooth surface is obtained by adopting a precise manual polishing method, the friction coefficient reaches 0.10, and the hard alloy is compared with the conventional WC-15 wt% Co- (Ni) - (Cr)3C2) The (VC) hard alloy is equivalent.
Taking an alloy block of 6mm multiplied by 10mm multiplied by 20mm, heating the alloy block to 900 ℃ in a muffle furnace, preserving the temperature for 20min, taking the alloy block out, naturally cooling the alloy block in the air, and obtaining the alloy block with the oxidation weight gain of 6.5mg cm-2·h-1Compared with the conventional WC-15 wt% Co- (Ni) - (Cr3C2) - (VC) hard alloy, the oxidation weight is increased by 85 mg-cm-2·h-1The reduction is more than 90 percent; the high-temperature thermal expansion instrument is adopted to detect that the 700 ℃ thermal expansion coefficient is 9.8 multiplied by 10-6/° C, more conventional WC-15 wt% Co- (Ni) - (Cr)3C2) The coefficient of thermal expansion of (VC) cemented carbide is 7.1 x 10-6Higher than 30% at/deg.C.
Example 2
High-temperature-resistant chromium carbide-based cemented carbide with high thermal expansion coefficientGold, the raw material of which is Ni powder with FSSS granularity of 2.5 mu m and Cr with FSSS granularity of 1.0 mu m3C2Powder, WC powder with FSSS granularity of 4.0 μm, PbO powder with FSSS granularity of 3.0 μm, 13% of Ni and Cr3C235% by mass of WC, 47% by mass of PbO, 5% by mass of PbO and 3.8% by mass of paraffin forming agent powder in addition to form a mixture;
grinding the mixture;
drying the mixture;
sieving the mixture;
compressing the mixture;
semi-processing the mixture compact;
sintering the mixture in a dewaxing-sintering integrated low pressure furnace under an argon atmosphere at a pressure of 50bar and at a temperature of 1340 ℃;
and (5) annealing and fine processing the sintered mixture compact to obtain a finished product.
The hardness of the hard alloy is HRA89.2, a smooth surface is obtained by adopting a precise manual polishing method, the friction coefficient reaches 0.11, and the hard alloy is equivalent to the conventional WC-13 wt% Co- (Ni) - (Cr3C2) - (VC) hard alloy.
Taking an alloy block of 6mm multiplied by 10mm multiplied by 20mm, heating the alloy block to 900 ℃ in a muffle furnace, preserving the temperature for 20min, taking the alloy block out, naturally cooling the alloy block to room temperature in the air, and obtaining the oxidation weight gain of 8.5mg cm-2·h-1Compared with the conventional WC-13 wt% Co- (Ni) - (Cr3C2) - (VC) hard alloy, the oxidation weight is increased by 80mg cm-2·h-1The reduction is more than 85 percent; the high-temperature thermal expansion instrument is adopted to detect that the 700 ℃ thermal expansion coefficient is 10.0 multiplied by 10-6V. C, more conventional WC-13 wt% Co- (Ni) - (Cr)3C2) The coefficient of thermal expansion of (VC) cemented carbide is 6.9 x 10-6The temperature is higher than 40 percent.
Example 3
A high-temp-resistant Cr-carbide-base hard alloy with high thermal expansion coefficient is prepared from Ni powder (FSSS granularity 2.5 microns) and Cr (FSSS granularity 1.0 micron)3C2Powder, WC powder with FSSS granularity of 4.0 μm, PbO powder with FSSS granularity of 5.0 μm, 15% of Ni and Cr3C238 percent of WC and 40 percent of PbO by mass7, an additional 4.0% by mass of a paraffin former powder to form a mixture;
grinding the mixture;
drying the mixture;
sieving the mixture;
compressing the mixture;
semi-processing the mixture compact;
sintering the mixture in a dewaxing-sintering integrated low pressure furnace at a temperature of 1320 ℃ under an argon atmosphere at a pressure of 50 bar;
and (5) annealing and fine processing the sintered mixture compact to obtain a finished product.
The hard alloy hardness HRA88.9 is detected to be 6mm multiplied by 12mm multiplied by 15mm alloy blocks which are taken to obtain smooth surfaces by adopting a precise manual polishing method, the friction coefficient reaches 0.13, and the hard alloy hardness HRA is equivalent to that of the conventional WC-15 wt% Co- (Ni) - (Cr3C2) - (VC) hard alloy.
Taking an alloy block of 6mm multiplied by 10mm multiplied by 20mm, heating the alloy block to 900 ℃ in a muffle furnace, preserving the temperature for 20min, taking the alloy block out, naturally cooling the alloy block to the room temperature in the air, and obtaining the oxidation weight gain of 7.8mg cm-2·h-1Compared with the conventional WC-15 wt% Co- (Ni) - (Cr3C2) - (VC) hard alloy, the oxidation weight gain of 85mg cm-2 h-1 is reduced by more than 90%; the high-temperature thermal expansion instrument is adopted to detect that the thermal expansion coefficient at 700 ℃ is 10.5 multiplied by 10-6/° C, more conventional WC-15 wt% Co- (Ni) - (Cr)3C2) The coefficient of thermal expansion of (VC) cemented carbide is 7.1 x 10-6The temperature is higher than 40 percent.
Claims (3)
1. The raw materials of the high-temperature-resistant high-thermal-expansion-coefficient hard alloy are nickel powder with the particle size of FSSS being 0.5-3.0 mu m, chromium carbide powder with the particle size of FSSS being 0.5-3.0 mu m, tungsten carbide powder with the particle size of FSSS being 1.0-6.0 and lead oxide powder with the particle size of FSSS being 1.0-5.0 mu m.
2. A high temperature resistant high thermal expansion coefficient cemented carbide according to claim 1 wherein: the raw materials comprise the following components in percentage by mass:
the mass percentage of the nickel powder is 10-18%;
the mass ratio of the chromium carbide powder is 25-40%;
the mass percentage of the tungsten carbide powder is 35-55%;
the mass percentage of the lead oxide powder is 2-10%.
3. A high temperature resistant high thermal expansion coefficient cemented carbide according to claim 1 wherein: the preparation method of the hard alloy comprises the following steps: providing 10-20% by mass of nickel powder, 25-40% by mass of chromium carbide powder, 35-55% by mass of tungsten carbide powder, 2-10% by mass of lead oxide powder and 3.5-4.5% by mass of paraffin powder to form a mixture;
grinding the mixture;
drying the mixture;
sieving the mixture;
compressing the mixture;
semi-processing the mixture compact;
sintering the mixture in a dewaxing-sintering integrated low-pressure furnace at a temperature of 1280-1380 ℃ under a pressure of 40-80bar argon atmosphere;
and (5) annealing and fine processing the sintered mixture compact to obtain a finished product.
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Application publication date: 20210810 |