WO2018120980A1 - Matériau d'outil de coupe en céramique autolubrifiant supplémenté d'une poudre composite de fluorure de calcium revêtu d'alliage de nickel-phosphore et procédé de préparation associé - Google Patents

Matériau d'outil de coupe en céramique autolubrifiant supplémenté d'une poudre composite de fluorure de calcium revêtu d'alliage de nickel-phosphore et procédé de préparation associé Download PDF

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WO2018120980A1
WO2018120980A1 PCT/CN2017/105471 CN2017105471W WO2018120980A1 WO 2018120980 A1 WO2018120980 A1 WO 2018120980A1 CN 2017105471 W CN2017105471 W CN 2017105471W WO 2018120980 A1 WO2018120980 A1 WO 2018120980A1
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solution
caf
powder
self
nickel
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许崇海
李智亮
吴光永
衣明东
肖光春
陈照强
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齐鲁工业大学
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Definitions

  • the invention relates to a self-lubricating ceramic tool material with a nickel-phosphorus alloy coated calcium fluoride composite powder and a preparation method thereof, and belongs to the technical field of ceramic tool materials.
  • the traditional self-lubricating ceramic tool material is prepared by directly mixing ceramic powder and solid lubricant powder, and then forming a block material through a certain molding and sintering process.
  • the direct addition of solid lubricants has two effects on the ceramic tool material: on the one hand, the solid lubricant in the tool material forms a self-lubricating film on the tool surface during the cutting process, thereby reducing the friction between the tool and the chip. Coefficients; on the other hand, solid lubricants have low strength and hardness, and dispersion in the tool material results in a decrease in mechanical properties, which in turn reduces the wear resistance of the tool.
  • Al 2 O 3 /TiC-based self-lubricating ceramic materials with three solid lubricants of MoS 2 , h-BN and CaF 2 have been reported in the literature.
  • MoS 2 decomposes during hot pressing and causes the material to generate more pores, resulting in very low mechanical properties
  • Al 2 O 3 /TiC/ h-BN self-lubricating ceramic material h-BN chemically reacts with Al 2 O 3 to form AlN during hot pressing, resulting in a large number of cracks, greatly reducing the mechanical properties of the material
  • Al 2 O 3 /TiC/CaF 2 Self-lubricating ceramic materials CaF 2 did not undergo obvious chemical reaction during sintering, but its mechanical properties were still significantly lower than those of Al 2 O 3 /TiC ceramic materials without solid lubricant. See Materials Science and Technology, 2006, 14(1): 5-8. It can be seen that the traditional self-lubricating
  • CN104045351A discloses alumina-coated calcium fluoride powder for self-lubricating tool materials, The aluminum nitrate and CaF 2 are used as raw materials, and are prepared by non-uniform nucleation method and vacuum calcination method for preparing self-lubricating tool materials;
  • CN104045325A discloses a self-lubricating tool material for adding coated calcium fluoride powder, which is Self-lubricating of Al 2 O 3 /(W,Ti)C/CaF 2 prepared by ball-milling aluminum hydroxide-coated calcium fluoride powder with alumina, tungsten carbide, nickel oxide and magnesium oxide powder by ball milling and hot pressing sintering Tool material.
  • the coating materials of the coated calcium fluoride powder disclosed in CN104045351A and CN104045325A above are ceramics, and the improvement of the hardness and bending strength of the prepared self-lubricating ceramic cutter is large (increased by 21.7% and 10.7, respectively). %), the improvement of fracture toughness is less (increased by 8%).
  • the fracture toughness of ceramic tool materials is a more important factor restricting its popularization and application. Improving the fracture toughness of ceramic tool materials has become a major technical problem in the industry.
  • Chinese patent document CN104962110A provides a nickel-boron-coated calcium fluoride composite powder for self-lubricating tool materials for preparing Al 2 O 3 /TiB 2 /CaF 2 self-lubricating tool materials.
  • the invention achieves an improvement in the fracture toughness of the ceramic tool material, the improvement in bending strength and hardness is not satisfactory.
  • the patent document adopts ultrasonic electroless plating method to prepare nickel-boron-coated calcium fluoride composite powder.
  • the electroless plating reducing agent sodium borohydride has a high price, and it is necessary to keep the pH of the plating solution at 12 or more, otherwise the decomposition will be deactivated, resulting in difficulty in maintaining the plating solution and high production cost;
  • the electroless plating solution The pH value is between 13-14, and the electroless plating temperature is between 55-75 °C. The high pH value and high temperature of the plating solution make the operating environment worse, and the treatment of the waste liquid after electroless plating is more difficult, which is not good for personnel health and environmental protection. .
  • the present invention provides a self-lubricating ceramic tool material which is coated with a nickel-phosphorus alloy coated calcium fluoride composite powder and a preparation method thereof.
  • a self-lubricating ceramic tool material with nickel-phosphorus alloy coated calcium fluoride composite powder is made of ⁇ -phase alumina ( ⁇ -Al 2 O 3 ) as matrix and tungsten carbide tungsten ((W, Ti) C)
  • ⁇ -phase alumina ⁇ -Al 2 O 3
  • tungsten carbide tungsten (W, Ti) C)
  • a nickel-phosphorus alloy coated calcium fluoride (CaF 2 @Ni-P) composite powder is used as a solid lubricant
  • magnesium oxide (MgO) is used as a sintering aid, which is formed by ball milling and hot pressing sintering.
  • the mass percentage of each component is: ⁇ -Al 2 O 3 30-48%, (W, Ti) C 42-66.5%, CaF 2 @Ni-P is based on the mass of CaF 2 in the composite powder 3 -12%, MgO 0.4-1.5%; among them,
  • Nickel-phosphorus alloy coated calcium fluoride is prepared as follows:
  • the CaF 2 powder is washed with a sodium hydroxide solution, and then a mixed solution of hydrofluoric acid and ammonium fluoride is added for coarsening, and the coarsened CaF 2 powder is ultrasonically oscillated by adding a sensitizing-activating solution, the sensitizing-activating solution
  • the composition is: palladium chloride (PdCl 2 ) 0.5-1g / L, stannous chloride dihydrate (SnCl 2 ⁇ 2H 2 O) 30-60g / L, sodium chloride (NaCl) 160-250g / L, a mass fraction of 35-37% concentrated hydrochloric acid 60-100ml / L, the balance is distilled water;
  • the sensitized-activated CaF 2 powder is added to the electroless plating solution, and is applied under ultrasonic vibration at 35-45 ° C, and the concentrated ammonia water with a mass fraction of 25-28% is added at any time to maintain the pH of the plating solution at 8.5.
  • the composition of the electroless plating solution is: nickel sulfate hexahydrate (NiSO 4 ⁇ 6H 2 O) 20-30 g / L, sodium citrate dihydrate (Na 3 C 6 H 5 O 7 ⁇ 2H 2 O) 40-60g/L, ammonium chloride (NH 4 Cl) 25-40g/L, sodium hypophosphite monohydrate (NaH 2 PO 2 ⁇ H 2 O) 25-35g/L, mass fraction 25-28%
  • the pH of the ammonia water is adjusted to 8.5-9.5, and the balance is distilled water; after plating, separation, washing and drying are performed to obtain a nickel-phosphorus alloy coated calcium fluoride (CaF 2 @Ni-P).
  • the raw material powders of the above components are all commercially available products, and the average particle diameters of the ⁇ -Al 2 O 3 powder, the (W, Ti) C powder, the CaF 2 powder, and the MgO powder.
  • the purity is 0.5-1 ⁇ m, 1-3 ⁇ m, 1-5 ⁇ m, and 1-2 ⁇ m, respectively, and the purity is more than 99%.
  • the self-lubricating ceramic tool material of the above-mentioned nickel-phosphorus alloy coated calcium fluoride composite powder has a mass percentage of each component: ⁇ -Al 2 O 3 31-45%, (W, Ti) C 45-64%, CaF 2 @Ni-P is 3-9% by mass of CaF 2 in the composite powder, and MgO is 0.5-1%; the sum of the components is 100%.
  • the self-lubricating ceramic tool material of the nickel-phosphorus alloy coated calcium fluoride composite powder has a mass percentage of each component: ⁇ -Al 2 O 3 31-32%, (W, Ti C 62-63%, CaF 2 @Ni-P is 5-5.5% by mass of CaF 2 in the composite powder, and MgO is 0.5%; the sum of the components is 100%.
  • a method for preparing a self-lubricating ceramic tool material by adding a nickel-phosphorus alloy coated calcium fluoride composite powder comprises the following steps:
  • step (3) Pour the multiphase suspension obtained in the step (2) into a ball mill tank, add the cemented carbide grinding ball at a weight ratio of 8-10:1, and perform ball milling with a nitrogen or argon atmosphere for 45-50 hours. ;
  • the washed CaF 2 powder is added to a hydrofluoric acid-ammonium fluoride roughening solution for coarsening, ultrasonically shaken for 10-20 min, centrifuged and washed with distilled water until neutral;
  • the roughened CaF 2 powder is added to the sensitization-activation solution, ultrasonically shaken for 10-20 min, centrifuged and washed with distilled water until neutral, and dried in a vacuum drying oven at 100-110 ° C for 5-8 h;
  • the components of the sensitization-activation solution are: palladium chloride (PdCl 2 ) 0.5-1 g/L, stannous chloride dihydrate (SnCl 2 ⁇ 2H 2 O) 30-60 g/L, sodium chloride (NaCl) 160-250g / L, the mass fraction of 35-37% concentrated hydrochloric acid 60-100ml / L, the balance is distilled water.
  • step (6) Adding the sensitized-activated CaF 2 powder to the electroless plating solution in step (6), performing electroless plating in a constant temperature water bath at 35-45 ° C, maintaining ultrasonic vibration during the plating process and dropping the mass at any time.
  • the concentration of 25-28% concentrated ammonia water keeps the pH of the plating solution at 8.5-9.5;
  • the composition of the electroless plating solution is: nickel sulfate hexahydrate (NiSO 4 ⁇ 6H 2 O) 20-30g/L, dihydrate Sodium citrate (Na 3 C 6 H 5 O 7 ⁇ 2H 2 O) 40-60 g/L, ammonium chloride (NH 4 Cl) 25-40 g/L, sodium monophosphite monohydrate (NaH 2 PO 2 ⁇ H 2 O) 25-35g / L, the mass fraction of 25-28% concentrated ammonia water adjusted pH 8.5-9.5, the balance is distilled water.
  • the solid particles are centrifuged and washed with distilled water until neutral, and then dried in a vacuum drying oven at 100-110 ° C for 8-10 h to obtain a CaF 2 @Ni-P composite powder;
  • the ball mill obtained in the step (8) is dried at 80-100 ° C for 20-30 h, and then passed through a 100-200 mesh sieve to obtain a mixed powder, which is sealed for use;
  • the mixed powder obtained in the step (9) is placed in a graphite mold, and after cold press forming, it is placed in a vacuum hot press sintering furnace for hot press sintering.
  • the sintering process parameters of the step (10) are: a heating rate of 10-20 ° C / min, a holding temperature of 1500-1600 ° C, a holding time of 10-20 min, and a hot pressing pressure of 25-30 MPa.
  • the sodium hydroxide solution for washing according to the step (4) is a sodium hydroxide solution having a mass fraction of 10% to 15%, and more preferably, the addition of CaF 2 powder per liter of the sodium hydroxide solution during the cleaning is added.
  • the amount is 30-70 g, which is recorded as 30-70 g/L.
  • the hydrofluoric acid-ammonium fluoride crude solution according to the step (5) is a mixed solution of ammonium fluoride and a hydrofluoric acid having a mass fraction of 35-40%, wherein the ammonium fluoride is 2-4 g. /L, the mass fraction of 35-40% hydrofluoric acid is 90-120ml / L.
  • the preparation of the hydrofluoric acid-ammonium fluoride roughening liquid and the coarsening of the CaF 2 powder should be carried out in a plastic container; further preferably, when coarsening, the CaF 2 powder is added in an amount of 30-70 g/L, that is, each The hydrofluoric acid-ammonium fluoride crude solution was added to 30-70 g of CaF 2 powder.
  • the CaF 2 powder is added in an amount of 30 to 60 g/L. That is, 30-60 g of CaF 2 powder is added per liter of the sensitization-activation solution.
  • the sensitizing-activation liquid preparation step described in the step (6) is as follows:
  • the CaF 2 powder is added in an amount of 4 to 9 g/L during the electroless plating in the step (7), that is, 4 to 9 g of CaF 2 powder is added per liter of the electroless plating solution.
  • the step of preparing the electroless plating solution described in the step (7) is as follows:
  • NiSO 4 ⁇ 6H 2 O, Na 3 C 6 H 5 O 7 ⁇ 2H 2 O, NH 4 Cl, NaH 2 PO 2 ⁇ H 2 O were weighed in proportion, and dissolved in an appropriate amount of distilled water to obtain a clear solution.
  • the chemical reagents such as sodium hydroxide and hydrofluoric acid used in the present invention are all commercially available products and are analytically pure, wherein the concentration of hydrofluoric acid is 35-40% by mass, and the concentration of concentrated hydrochloric acid is 35-37. %, the concentration of concentrated ammonia is 25-28% by mass.
  • the invention prepares a self-lubricating ceramic tool material by adding a nickel-phosphorus alloy coated calcium fluoride composite powder (CaF 2 @Ni-P) instead of the CaF 2 powder as a solid lubricant, on the one hand, the coating layer Ni-P
  • the alloy can accelerate the sintering densification process of the solid lubricant and the ceramic matrix, prevent the abnormal growth of the crystal grains, and improve the microstructure of the self-lubricating ceramic tool material; on the other hand, the coating Ni-P alloy can be used for the self-lubricating ceramic tool
  • the material is toughened and strengthened, and at the same time, its mechanical properties are improved, thereby improving the wear resistance of the self-lubricating ceramic tool.
  • the invention has a great improvement on the fracture toughness of the self-lubricating ceramic tool material, and is more beneficial to Popularization and application of ceramic tool materials.
  • the present invention first cleans and roughens the calcium fluoride powder prior to electroless plating, especially the roughening step. It is beneficial to increase the bonding force between the metal plating layer and the calcium fluoride powder, thereby improving the strengthening effect of the plating metal on the calcium fluoride; on the other hand, the invention simplifies the sensitization-activation one-step method for the calcium fluoride powder. Sensitization and activation process ensure the consistency of quality of different batches of products, which is suitable for mass production.
  • the pH of the electroless plating solution is controlled at 8.5-9.5.
  • the temperature is controlled at 35-45 ° C.
  • the lower pH and temperature of the electroless plating solution improve the operating environment of the electroless plating, reduce the difficulty of processing the waste liquid after electroless plating, and lower the production cost, which is beneficial to health and environmental protection.
  • FIG. 1 is a scanning electron microscope (SEM) photograph of a CaF 2 raw material powder used in an embodiment of the present invention.
  • Example 2 is a SEM photograph of a CaF 2 @Ni-P composite powder prepared in Example 1 of the present invention.
  • Fig. 3 is an X-ray diffraction spectrum of a CaF 2 @Ni-P composite powder and a CaF 2 raw material powder prepared in Example 1 of the present invention.
  • Fig. 4 is an X-ray energy spectrum of a CaF 2 @Ni-P composite powder prepared in Example 1 of the present invention.
  • Figure 5 is a cross-sectional SEM photograph of a self-lubricating ceramic tool material added with CaF 2 @Ni-P composite powder prepared in Example 1 of the present invention.
  • Figure 6 is a cross-sectional SEM photograph of a self-lubricating ceramic tool material prepared by adding a CaF 2 powder prepared in a comparative example of Example 1 of the present invention.
  • the raw material powders used in the examples are all commercially available products, and the average particle diameters of ⁇ -Al 2 O 3 powder, (W, Ti) C powder, CaF 2 powder, and MgO powder are 0.5 ⁇ m and 2.5, respectively. ⁇ m, 5 ⁇ m and 2 ⁇ m, all of which are more than 99% pure.
  • the chemical reagents used in the examples were all commercially available products and analyzed analytically, wherein the concentration of hydrofluoric acid was 40% by mass, the concentration of concentrated hydrochloric acid was 37% by mass, and the concentration of concentrated ammonia was 28% by mass.
  • Example 1 A self-lubricating ceramic tool material to which CaF 2 @Ni-P composite powder was added, the mass percentage of each component was: ⁇ -Al 2 O 3 31.8%, (W, Ti) C 62.5%, CaF 2 @Ni-P is 5.2% by mass of CaF 2 in the composite powder, and MgO is 0.5%.
  • the preparation method is as follows:
  • step (3) The multiphase suspension obtained in the step (2) was poured into a ball mill tank, 900 g of a cemented carbide grinding ball was added, and ball milling was carried out for 48 hours under a nitrogen atmosphere.
  • the solution was clarified; the NiSO 4 ⁇ 6H 2 O solution was slowly added to the Na 3 C 6 H 5 O 7 ⁇ 2H 2 O solution, and stirred while stirring to obtain a solution a; the NH 4 Cl solution was slowly added to the solution a while adding While stirring, the solution b is obtained; the NaH 2 PO 2 ⁇ H 2 O solution is slowly added to the solution b, and stirred while stirring to obtain a solution c; the concentrated ammonia water is slowly added dropwise to the solution c, and the solution is stirred while stirring. The pH reached 9.5, and then distilled water was added to 1000 ml and stirred to obtain an electroless plating solution.
  • the sensitized-activated CaF 2 powder was added to an electroless plating solution, and electroless plating was performed in a constant temperature water bath at 45 °C.
  • the ultrasonic vibration was maintained during the plating process and concentrated ammonia was added dropwise at any time to maintain the pH of the plating solution at 9.5.
  • the solid particles were centrifuged and washed with distilled water until neutral, and then dried in a vacuum oven at 100 ° C for 10 hours to obtain a CaF 2 @Ni-P composite powder.
  • the ball mill obtained in the step (8) is dried in a vacuum drying oven at 100 ° C for 24 hours, and then passed through a 120 mesh sieve to obtain a mixed powder, which is sealed for use.
  • the mixed powder obtained in the step (9) is placed in a graphite mold, and after cold press forming, it is placed in a vacuum hot press sintering furnace for hot press sintering.
  • the sintering process parameters are: heating rate 15 ° C / min, holding temperature 1550 ° C, holding time 15 min, hot pressing pressure 25 MPa.
  • Comparative Example 1 A self-lubricating ceramic tool material to which CaF 2 powder was added, the mass percentage of each component was: ⁇ -Al 2 O 3 31.8%, (W, Ti) C 62.5%, CaF 2 5.2%, MgO 0.5%.
  • the preparation method is as follows:
  • step (3) The multiphase suspension obtained in the step (2) was poured into a ball mill tank, 900 g of a cemented carbide grinding ball was added, and ball milling was carried out for 48 hours under a nitrogen atmosphere.
  • the ball mill obtained in the step (4) is dried in a vacuum drying oven at 100 ° C for 24 hours, and then passed through a 120 mesh sieve to obtain a mixed powder, which is sealed for use.
  • the mixed powder obtained in the step (5) is charged into a graphite mold, and after cold press forming, it is placed in a vacuum hot press sintering furnace for hot press sintering.
  • the sintering process parameters are: heating rate 15 ° C / min, holding temperature 1550 ° C, holding time 15 min, hot pressing pressure 25 MPa.
  • the CaF 2 raw material powder is an irregular polyhedron with sharp edges and a smooth surface.
  • the CaF 2 @Ni-P composite powder is round and blunt, and the surface is rough due to the coating of closely arranged spherical particles.
  • the X-ray energy spectrum of the CaF 2 @Ni-P composite powder in Fig. 4 has only Ni and P elements except for the F and Ca elements, indicating that the above amorphous alloy is a Ni-P alloy. 2, 3 and 4, it can be seen that the composite powder of Ni-P alloy coated CaF 2 can be successfully prepared according to the method of the present invention. It can be seen from Fig. 5 that the self-lubricating ceramic tool material with CaF 2 @Ni-P composite powder has uniform grain size and tight arrangement. It can be seen from Fig. 6 that the self-lubricating ceramic tool material with CaF 2 powder has uneven grain size. There is an abnormal growth. Figures 5 and 6 show that the addition of a nickel-phosphorus alloy coated calcium fluoride composite powder instead of the calcium fluoride powder as a solid lubricant can improve the microstructure of the self-lubricating ceramic tool material.
  • the mechanical properties of the self-lubricating ceramic tool material prepared by adding the CaF 2 @Ni-P composite powder prepared in Example 1 were: bending strength 582 MPa, hardness 14.1 GPa, fracture toughness 4.3 MPa ⁇ m 1/2 ;
  • the mechanical properties of the self-lubricating ceramic tool material prepared by adding CaF 2 powder are: bending strength 506 MPa, hardness 13.4 GPa, and fracture toughness 3.6 MPa ⁇ m 1/2 . It can be seen that the flexural strength, hardness and fracture toughness of the former are increased by 15.0%, 5.2% and 19.4%, respectively.
  • Example 2 Self-lubricating ceramic tool material with CaF 2 @Ni-P composite powder added, the mass percentage of each component is: ⁇ -Al 2 O 3 32.6%, (W, Ti) C 63.9%, CaF 2 @Ni-P is 3% by mass of CaF 2 in the composite powder, and MgO is 0.5%.
  • the preparation method is as follows:
  • step (3) The multiphase suspension obtained in the step (2) was poured into a ball mill tank, and 950 g of a cemented carbide grinding ball was added, and ball milling was carried out for 45 hours under a nitrogen atmosphere.
  • the ball mill obtained in the step (8) is dried in a vacuum drying oven at 100 ° C for 20 h, and then passed through a 120 mesh sieve to obtain a mixed powder, which is sealed for use.
  • the mixed powder obtained in the step (9) is placed in a graphite mold, and after cold press forming, it is placed in a vacuum hot press sintering furnace for hot press sintering.
  • the sintering process parameters are: heating rate 10 ° C / min, holding temperature 1500 ° C, holding time 10 min, hot pressing pressure 30 MPa.
  • Comparative Example 2 A self-lubricating ceramic tool material to which CaF 2 powder was added, the mass percentage of each component was: ⁇ -Al 2 O 3 32.6%, (W, Ti) C 63.9%, CaF 2 3%, MgO 0.5%.
  • the preparation method is as follows:
  • step (3) The multiphase suspension obtained in the step (2) was poured into a ball mill tank, and 950 g of a cemented carbide grinding ball was added, and ball milling was carried out for 45 hours under a nitrogen atmosphere.
  • the ball mill obtained in the step (4) is dried in a vacuum drying oven at 100 ° C for 20 h, and then passed through a 120 mesh sieve to obtain a mixed powder, which is sealed for use.
  • the mixed powder obtained in the step (5) is charged into a graphite mold, and after cold press forming, it is placed in a vacuum hot press sintering furnace for hot press sintering.
  • the sintering process parameters are: heating rate 10 ° C / min, holding temperature 1500 ° C, holding time 10 min, hot pressing pressure 30 MPa.
  • the mechanical properties of the self-lubricating ceramic tool material prepared by adding the CaF 2 @Ni-P composite powder prepared in Example 2 were as follows: bending strength 591 MPa, hardness 15.2 GPa, fracture toughness 4.6 MPa ⁇ m 1/2 ; 2
  • the mechanical properties of the self-lubricating ceramic tool material prepared by adding CaF 2 powder are: bending strength 534 MPa, hardness 14.5 GPa, and fracture toughness 3.9 MPa ⁇ m 1/2 . It can be seen that the flexural strength, hardness and fracture toughness of the former are increased by 10.7%, 4.8% and 17.9%, respectively.
  • Example 3 Self-lubricating ceramic tool material with CaF 2 @Ni-P composite powder added, the mass percentage of each component is: ⁇ -Al 2 O 3 44.4%, (W, Ti) C 45.6%, CaF 2 @Ni-P is 9% by mass of CaF 2 in the composite powder, and MgO1%.
  • the preparation method is as follows:
  • step (3) The multiphase suspension obtained in the step (2) was poured into a ball mill tank, and 850 g of a cemented carbide grinding ball was added, and ball milling was carried out for 50 hours under a nitrogen atmosphere.
  • Clarify the solution slowly add NiSO 4 ⁇ 6H 2 O solution to Na 3 C 6 H 5 O 7 ⁇ 2H 2 O solution, while stirring, to obtain solution a; slowly add NH 4 Cl solution to solution a, while adding While stirring, the solution b is obtained; the NaH 2 PO 2 ⁇ H 2 O solution is slowly added to the solution b, and stirred while stirring to obtain a solution c; the concentrated ammonia water is slowly added dropwise to the solution c, and the solution is stirred while stirring. The pH reached 8.5, and then distilled water was added to 1000 ml and stirred to obtain an electroless plating solution.
  • the sensitized-activated CaF 2 powder was added to an electroless plating solution, and electroless plating was performed in a constant temperature water bath at 40 °C.
  • the ultrasonic vibration was maintained during the plating process and concentrated ammonia was added dropwise at any time to maintain the pH of the plating solution at 8.5.
  • the solid particles were centrifuged and washed with distilled water until neutral, and then dried in a vacuum oven at 100 ° C for 10 hours to obtain a CaF 2 @Ni-P composite powder.
  • the ball mill obtained in the step (8) is dried in a vacuum drying oven at 90 ° C for 30 hours, and then passed through a 100 mesh sieve to obtain a mixed powder, which is sealed and used.
  • the mixed powder obtained in the step (9) is placed in a graphite mold, and after cold press forming, it is placed in a vacuum hot press sintering furnace for hot press sintering.
  • the sintering process parameters are: heating rate 15 ° C / min, holding temperature 1600 ° C, holding time 20 min, hot pressing pressure 30 MPa.
  • Comparative Example 3 A self-lubricating ceramic tool material to which CaF 2 powder was added, the mass percentage of each component was: ⁇ -Al 2 O 3 44.4%, (W, Ti) C 45.6%, CaF 2 9%, MgO 1%.
  • the preparation method is as follows:
  • step (3) The multiphase suspension obtained in the step (2) was poured into a ball mill tank, and 850 g of a cemented carbide grinding ball was added, and ball milling was carried out for 50 hours under a nitrogen atmosphere.
  • the ball mill obtained in the step (4) is dried in a vacuum drying oven at 90 ° C for 30 hours, and then passed through a 100 mesh sieve to obtain a mixed powder, which is sealed and used.
  • the mixed powder obtained in the step (5) is charged into a graphite mold, and after cold press forming, it is placed in a vacuum hot press sintering furnace for hot press sintering.
  • the sintering process parameters are: heating rate 15 ° C / min, holding temperature 1600 ° C, holding time 20 min, hot pressing pressure 30 MPa.
  • the mechanical properties of the self-lubricating ceramic tool material prepared by adding the CaF 2 @Ni-P composite powder prepared in Example 3 were: bending strength 563 MPa, hardness 13.7 GPa, fracture toughness 3.8 MPa ⁇ m 1/2 ; 3
  • the mechanical properties of the prepared self-lubricating ceramic tool material with CaF 2 powder are: bending strength 491 MPa, hardness 12.9 GPa, fracture toughness 3.2 MPa ⁇ m 1/2 . It can be seen that the flexural strength, hardness and fracture toughness of the former are increased by 14.7%, 6.2% and 18.8%, respectively.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Powder Metallurgy (AREA)
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Abstract

La présente invention concerne un matériau d'outil de coupe en céramique auto-lubrifiant auquel est ajoutée une poudre composite de fluorure de calcium revêtu d'un alliage de nickel-phosphore et son procédé de préparation. Le matériau d'outil de coupe en céramique auto-lubrifiant est constitué de : 30 à 48 % d'α‑Al2O3, 42 à 66,5 % de (W, Ti) C, 3 à 12 % de CaF2@Ni‑P en masse de CaF2, et 0,4 à 1,5 % de MgO. Le procédé de préparation de CaF2@Ni‑P comprend : le grossissement des poudres de CaF2 après leur nettoyage, l'ajout aux poudres de CaF2 grossies d'un liquide d'activation de sensibilisation et la réalisation d'une vibration ultrasonore, puis la réalisation d'un placage chimique dans des conditions d'une valeur de pH de 8,5 à 9,5, d'une température de 35 à 45 °C et d'une vibration ultrasonore.
PCT/CN2017/105471 2016-12-28 2017-10-10 Matériau d'outil de coupe en céramique autolubrifiant supplémenté d'une poudre composite de fluorure de calcium revêtu d'alliage de nickel-phosphore et procédé de préparation associé WO2018120980A1 (fr)

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CN109704770B (zh) * 2019-01-29 2021-10-22 齐鲁工业大学 添加镍包覆六方氮化硼纳米片复合粉体的自润滑陶瓷刀具材料及其制备方法
CN109721361B (zh) * 2019-01-29 2021-09-07 齐鲁工业大学 添加金属包覆纳米固体润滑剂复合粉体的自润滑陶瓷刀具材料及其制备方法

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