CN104018019B - A kind of ZrB2The preparation method of/Cu composite - Google Patents
A kind of ZrB2The preparation method of/Cu composite Download PDFInfo
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- CN104018019B CN104018019B CN201410221818.6A CN201410221818A CN104018019B CN 104018019 B CN104018019 B CN 104018019B CN 201410221818 A CN201410221818 A CN 201410221818A CN 104018019 B CN104018019 B CN 104018019B
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Abstract
The invention belongs to inorganic composite materials preparing technical field, be specifically related to a kind of ZrB2The preparation method of/Cu composite. The method comprises ZrB2The steps such as powder nickel plating, mixed grinding, hot pressed sintering. The present invention utilizes active element Ni and ZrB2Have wetability well, simultaneously Ni can form with Cu the feature of good solid solution, first by nickel chemical plating technology at ZrB2Powder surface plates layer of Ni, thereby effectively improves ZrB2Interface combination with Cu, adopts hot-pressing sintering technique afterwards, with the ZrB after nickel plating2With Cu powder be raw material, at lower temperature, prepare the ZrB of high-compactness2/Cu composite. Adopt the prepared ZrB of the present invention2/ Cu composite material combination property is good, while preparation, can effectively reduce loss and the replacement frequency of electrode, thereby have good social and economic effects for EDM processing with electrode.
Description
Technical field
The invention belongs to inorganic composite materials preparing technical field, be specifically related to a kind of ZrB2The preparation of/Cu compositeMethod.
Background technology
Spark machined (ElectricalDischargeMachining is called for short EDM) is to utilize to be immersed in working solutionTwo interpolar pulsed discharges time the galvanic action ablation conductive material that produces special process method, claim again electric discharge processing or galvanic corrosionProcessing, because its unique processing mechanism has adapted to the needs of production development, thereby is developed rapidly.
In spark machined, the performance of tool-electrode material directly affects the EDM Performance of electrode, as processingSpeed, tool loss rate, workpiece surface quality etc. In prior art, Cu-base composites has high strength, electric-conductivity heat-conductivity highEnergy and good wearability and high temperature stability performance, obtained widely in industries such as Aero-Space, electric apparatus, machine-buildingApplication, has become one of study hotspot on Material Field. And institute's developmental research is at present multiple for the copper base of EDM electrode materialCondensation material is mainly granule reinforced copper base composite material, it be by additional ceramic particle reinforced phase or spontaneous enter fine copper matrix orIn copper alloy, obtain having concurrently the electrical and thermal conductivity performance that toughness that fine copper is good is moulding, high and strengthen high strength hardness, the height of particleThe composite of fusing point and high-modulus performance.
ZrB2Be a kind of hexagonal structure material, because covalent bond, ionic bond and metallic bond exist simultaneously, and possess much excellentOptimum energy: high-melting-point (3245 DEG C), high strength, high rigidity, good electrical and thermal conductivity performance and corrosion resistance etc., multiple with CuClose, can, in the situation that ensureing that EDM processing needs, give material high strength and high hardness and good wear resistance, asA kind of new E DM tool-electrode, can obviously reduce the tool loss in process. But in prior art, due to ZrB2Poor with the wetability of metal Cu, in sintering, both interfaces, in conjunction with poor, are difficult to reach the compactness extent of expectation, and material is easily twoThe fracture of junction, person interface, thereby there is no a kind of ZrB preferably2/The technology of preparing of Cu composite.
Summary of the invention
The object of the present invention is to provide a kind of ZrB2The preparation method of/Cu composite, prepared ZrB2/ Cu is compoundMaterial can be used as the candidate material application of EDM electrode material, thereby it is serious to overcome existing electrode material loss, needs often moreThe problem of changing.
The technical solution used in the present invention is as follows:
A kind of ZrB2The preparation method of/Cu composite, comprises the following steps:
（1）ZrB2Powder Nickel Plating Treatment: get ZrB2Powder, carries out pretreatment according to the order of pickling, sensitization, activation, thenCarry out chemical nickel plating; ZrB after Nickel Plating Treatment2Powder is dry, for subsequent use under vacuum;
Described pickling adopts the HCl solution-treated that volume fraction is 37%;
Described sensitization adopts SnCl2-HCl solution-treated, wherein SnCl2·2H2O concentration is 0.1mol/L, the interpolation of HClAmount is 30ml/L;
Described activation adopts the silver ammino solution processing that concentration is 0.02mol/L;
In described chemical nickel plating plating solution used, taking nickel sulfate hexahydrate as main salt, sodium borohydride is as reducing agent, ethylenediamine is networkMixture, lead ion is stabilizing agent; Wherein NiSO4·6H2O concentration is 15g/L, NaBH4Concentration is 2g/L, and ethylenediamine concentration is100ml/L，Pb(NO3)2Concentration is 10mg/L.
Described chemical nickel plating is by ZrB2Powder is placed in chemical plating fluid, drips NaOH solution and regulates pH value >=10, at alkaliProperty is heated to more than 80 DEG C under environment, keeps 60min, carries out nickel plating;
(2) mixed grinding: by the ZrB after Nickel Plating Treatment in step (1)2Powder and Cu powder proportionally, mix, and grindMill, dry;
Described ZrB2Powder and Cu powder are counted by volume, and the volume ratio of the interpolation of Cu powder is 50 ~ 70%;
Described grinding adopts ball mill grinding, adds zirconium oxide balls and absolute ethyl alcohol so that grind evenly when grinding, grindsAfter mill, material adopts rotary evaporation mode to be dried;
(3) hot pressed sintering: step (2) material is incubated to 10 ~ 60min under 700 ~ 1000 DEG C, 10 ~ 40MPa pressure, burns50 ~ 150 DEG C/min of knot speed, hot pressed sintering, is prepared into ZrB2/ Cu composite;
Described sintering carries out under vacuum.
The present invention utilizes active element Ni and ZrB2Have wetability well, Ni can form good solid solution with Cu simultaneouslyThe feature of body, first by nickel chemical plating technology at ZrB2Powder surface plates layer of Ni, thereby effectively improves ZrB2Interface with CuIn conjunction with, adopt afterwards hot-pressing sintering technique, with the ZrB after nickel plating2With Cu powder be raw material, at lower temperature, prepare height and causeThe ZrB of density2/Cu composite. Detect the ZrB that adopts the method to prepare at 900 DEG C through actual2/ Cu composite, withContaining 60%Cu(volume content) ZrB2/ Cu sample is example, and its bending strength can reach 452MPa, and hardness can reach 5.6GPa, heatConductance is 251W/ (mK), and resistivity is 2.8 μ Ω cm, in end face frictional wear experiment, and mass loss before and after wearing and tearingLower, coefficient of friction is in 0.05 left and right, and wear surface is wear characteristic of adhesion, thereby high comprehensive performance.
In general, ZrB provided by the present invention2The preparation method of/Cu composite, has solved second-phase preferablyZrB2Problem with being combined in the interface of matrix material Cu, makes ZrB2Be combined better with matrix Cu, improved the structure of material, carryThe high performance of material; Prepare material temperature required lower simultaneously, be easy to realize; Prepared ZrB2/ Cu composite is comprehensiveFunction admirable, while preparation, can effectively reduce loss and the replacement frequency of electrode, thereby have for EDM processing with electrodeGood social and economic effects.
Brief description of the drawings
Fig. 1 is ZrB in the present invention2SEM figure before and after powder electroless nickel, before wherein a is nickel plating, after b is nickel plating;
Fig. 2 is embodiment 2 sintered sample ZrB2/The section SEM figure of Cu composite;
Fig. 3 is embodiment 2 sintered sample ZrB2The wear surface SEM figure of/Cu composite.
Detailed description of the invention
Below in conjunction with embodiment the present invention will be further explained explanation so that those skilled in the art can be betterImplement the present invention.
Embodiment 1
ZrB2The preparation method of/Cu composite, comprises the following steps:
（1）ZrB2Powder Nickel Plating Treatment: get ZrB2Powder, carries out pretreatment according to the order of pickling, sensitization, activation, thenCarry out chemical nickel plating; ZrB after Nickel Plating Treatment2Powder is dry, for subsequent use under vacuum;
Described pickling adopts HCl to process, by ZrB2It is 37% HCl solution that powder is placed in volume fraction, stirring at low speed30 minutes, carry out pickling; Powder after pickling is placed in absolute ethyl alcohol ultrasonic cleaning 10 minutes, then vacuum drying 4 hours;
Described sensitization adopts SnCl2Solution-treated, specifically refers to pickling, dried ZrB2Powder is placed in SnCl2-HClIn solution, stirring at low speed is done sensitization processing for 30 minutes; Described sensitization SnCl2SnCl in-HCl solution-treated2·2H2O concentration is 0.1Mol/L, the addition of HCl is 30ml/L;
Described activation adopts silver ammino solution processing, specifically refers to sensitization is processed to rear ZrB2Powder cleaning is to neutral, thenThe silver ammino solution that the concentration that is placed in fresh configuration is 0.02mol/L carries out activation processing, and soak time is 45 minutes, processesRear vacuum powder is dry;
In described chemical nickel plating plating solution used, taking nickel sulfate hexahydrate as main salt, sodium borohydride is as reducing agent, ethylenediamine is networkMixture, lead ion is stabilizing agent; Wherein NiSO4·6H2O concentration is 15g/L, NaBH4Concentration is 1g/L, and ethylenediamine concentration is100ml/L，Pb(NO3)2Concentration is 10mg/L;
Described chemical nickel plating is by ZrB2Powder is placed in chemical plating fluid, is heated to 80 DEG C under alkaline environment, drips NaOHSolution regulates pH value >=10, is heated to 80 DEG C under alkaline environment, keeps 60min, carries out nickel plating;
(2) mixed grinding: by the ZrB after Nickel Plating Treatment in step (1)2Powder and Cu powder proportionally, mix, and grindMill, dry;
ZrB after nickel plating in material2Mix with Cu, the volume fraction of Cu is 50%, wherein ZrB after nickel plating2Grain weight amount is 25g,Cu powder is 35g;
Described grinding adopts ball mill grinding, adds zirconium oxide balls and absolute ethyl alcohol so that grind evenly when grinding, grindsAfter mill, material adopts rotary evaporation mode to be dried;
(3) hot pressed sintering: take the 3.3g material mixing in step (2), pack into and be of a size of 32 × 4.5 × 3mm3Graphite grinding tool in carry out hot pressed sintering under vacuum atmosphere, pressure 10MPa, rises to 900 DEG C with the heating rate of 100 DEG C/minRear insulation 10min, obtains ZrB after naturally cooling2/ Cu composite.
In preparation process, to ZrB2Before and after powder chemical nickel plating, carry out electron-microscope scanning, its SEM schemes as shown in Figure 1, can from Fig. 1To find out, ZrB before chemical nickel plating2Powder surface is very smooth, after nickel plating, and ZrB2Powder surface has superscribed Ni coating equably.The ZrB that the present embodiment is prepared2/ Cu composite, its hardness after measured, can reach 5.8GPa.
Embodiment 2
The present embodiment is prepared ZrB2When/Cu composite, step is with embodiment 1, only ZrB in set-up procedure (2)2With Cu'sVolume ratio, the volume fraction of Cu is 60% to be, i.e. ZrB after nickel plating2Grain weight amount is 20g, and Cu powder is 40g; Heat in set-up procedure (3)While pressing sintering, pressure is 20MPa, and sintering temperature is 900 DEG C, and heating rate is 100 DEG C/min, and temperature retention time is 30min.
Prepared ZrB2The section SEM of/Cu composite schemes as shown in Figure 2, as can be seen from the figure material sample knotStructure densification, presents the fracture model that ductile rupture and brittle fracture combine. Fig. 3 is the ZrB of sintering2/ Cu composite sampleThe wear surface SEM figure of product, can find out that sample surfaces presents bed separation, the feature of adhesive wear, and surface has slightGroove occurs.
Embodiment 3
The present embodiment is prepared ZrB2When/Cu composite, step is with embodiment 1, only ZrB in set-up procedure (2)2With Cu'sVolume ratio, the volume fraction of Cu is 70%, i.e. ZrB after nickel plating2Grain weight amount is 15g, and Cu powder is 50g; Hot pressing in set-up procedure (3)When sintering, pressure is 30MPa, and sintering temperature is 900 DEG C, and heating rate is 100 DEG C/min, and temperature retention time is 45min.
By ZrB prepared the present embodiment2/ Cu composite carries out performance measurement, and its bending strength is 475MPa, heatDiffusion coefficient is 0.7781m2S, thermal conductivity is 270W/ (mK), and resistivity is 2.1 μ Ω cm, and electrical conductivity is 0.48×106S/cm。
Embodiment 4
The present embodiment is prepared ZrB2When/Cu composite, step, with embodiment 1, is pressed when the middle hot pressed sintering of set-up procedure (3)Power is 40MPa, and sintering temperature is 700 DEG C, and heating rate is 50 DEG C/min, and temperature retention time is 60min.
Embodiment 5
The present embodiment is prepared ZrB2When/Cu composite, step is with embodiment 1, only ZrB in set-up procedure (2)2With Cu'sVolume ratio, the volume fraction of Cu is 60%, i.e. ZrB after nickel plating2Grain weight amount is 20g, and Cu powder is 40g; Hot pressing in set-up procedure (3)When sintering, pressure is 20MPa, and sintering temperature is 800 DEG C, and heating rate is 100 DEG C/min, and temperature retention time is 40min.
Embodiment 6
The present embodiment is prepared ZrB2When/Cu composite, step is with embodiment 1, only ZrB in set-up procedure (2)2With Cu'sVolume ratio, the volume fraction of Cu is 70%, i.e. ZrB after nickel plating2Grain weight amount is 15g, and Cu powder is 50g; Hot pressing in set-up procedure (3)When sintering, pressure is 30MPa, and sintering temperature is 850 DEG C, and temperature retention time is 30min.
Embodiment 7
The present embodiment is prepared ZrB2When/Cu composite, step is with embodiment 1, only ZrB in set-up procedure (2)2With Cu'sVolume ratio, the volume fraction of Cu is 60%, i.e. ZrB after nickel plating2Grain weight amount is 20g, and Cu powder is 40g; Hot pressing in set-up procedure (3)When sintering, pressure is 20MPa, and sintering temperature is 850 DEG C, and heating rate is 150 DEG C/min, and temperature retention time is 15min.
Embodiment 8
The present embodiment is prepared ZrB2When/Cu composite, step is with embodiment 1, only ZrB in set-up procedure (2)2With Cu'sVolume ratio, the volume fraction of Cu is 60%, i.e. ZrB after nickel plating2Grain weight amount is 20g, and Cu powder is 40g; Hot pressing in set-up procedure (3)When sintering, pressure is 30MPa, and sintering temperature is 950 DEG C, and heating rate is 100 DEG C/min, and temperature retention time is 15min.
Embodiment 9
The present embodiment is prepared ZrB2When/Cu composite, step is with embodiment 1, only ZrB in set-up procedure (2)2With Cu'sVolume ratio, the volume fraction of Cu is 60%, i.e. ZrB after nickel plating2Grain weight amount is 20g, and Cu powder is 40g; Hot pressing in set-up procedure (3)When sintering, pressure is 20MPa, and sintering temperature is 950 DEG C, and heating rate is 150 DEG C/min, and temperature retention time is 10min.
Electroless plating method is in one of common method of ceramic powder surface clad or composite coating, its essence is oneAutocatalytic redox reaction process, the metal ion in plating solution is reduced into metallic and is deposited under catalytic actionOn powder surface, thereby obtain the certain thickness coat of metal. Due to compared with electroplating technology, it is equal that chemical plating has thickness of coatingEven, compact structure, the advantage such as voidage is low, simple to operate, and environmental pollution is little, thereby the present invention utilizes Ni and ZrB2Have goodThe feature of wetability, by adopting electroless plating method first active element Ni to be coated in to ZrB2Powder surface, then utilizes the Ni can be withCu forms the characteristic of unlimited solid solution, further adopts hot-pressing sintering method to prepare ZrB2/ Cu composite. Due to compoundIn material system, the introducing of Ni element, has improved ZrB2With the interface binding power of Cu, thereby prepared ZrB2/ Cu compositeThere is comparatively good material property, be suitable for preparing EDM processing electrode, can effectively reduce the loss and replacing frequency of electrodeRate, thereby there is good social and economic effects.
It should be noted that, above-described embodiment is all preferred embodiments of the present invention, but embodiments of the present invention alsoBe not subject to the restriction of above-mentioned specific embodiment, concrete material proportion, the sintering temperature parameter etc. on above-described embodiment basis, doneChange, all should think within the claimed scope of the present invention.
Claims (5)
1. a ZrB2The preparation method of/Cu composite, is characterized in that, the method comprises the following steps:
（1）ZrB2Powder Nickel Plating Treatment
Get ZrB2Powder, carries out pretreatment according to the order of pickling, sensitization, activation, then carries out chemical nickel plating; After Nickel Plating TreatmentZrB2Powder is dry, for subsequent use under vacuum;
Described chemical nickel plating is by ZrB2Powder is placed in chemical plating fluid, drips NaOH solution and regulates pH value >=10, at alkaline environmentUnder be heated to more than 80 DEG C, keep more than 60min, carrying out nickel plating;
(2) mixed grinding
By the ZrB after Nickel Plating Treatment in step (1)2Powder mixes with Cu powder, and the volume ratio of Cu powder is 50 ~ 70%, and powder mixesEvenly, grind, dry;
(3) hot pressed sintering
Step (2) material is warming up to 700 ~ 1000 DEG C with the sintering rate of 50 ~ 150 DEG C/min, under 10 ~ 40MPa pressure, protectsTemperature 10 ~ 60min, hot pressed sintering is prepared into ZrB2/ Cu composite.
2. ZrB as claimed in claim 12The preparation method of/Cu composite, is characterized in that, in step (1), described pickling is adoptedThe HCl that is 37% by volume fraction processes; Described sensitization adopts SnCl2-HCl solution-treated, wherein SnCl2·2H2O concentration is0.1mol/L, the addition of HCl is 30ml/L; Described activation adopts the silver ammino solution processing that concentration is 0.02mol/L.
3. ZrB as claimed in claim 12The preparation method of/Cu composite, is characterized in that, in step (1), and described chemical platingLiquid is made up of main salt nickel sulfate hexahydrate, borane reducing agent sodium hydride, complexing agent ethylenediamine, stabilizing agent lead ion; Wherein NiSO4·6H2O concentration is 15g/L, NaBH4Concentration is 2g/L, and ethylenediamine concentration is 100ml/L, Pb2+Concentration is 10mg/L.
4. ZrB as claimed in claim 12The preparation method of/Cu composite, is characterized in that, described in step (2), grinds and adoptsWith ball mill grinding, when grinding, add zirconium oxide balls and absolute ethyl alcohol so that grind evenly; After grinding, material adopts rotation to steamOriginating party formula is dried.
5. ZrB as claimed in claim 12The preparation method of/Cu composite, is characterized in that, described in step (3), sintering existsUnder vacuum, carry out.
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| CN106424713B (en) * | 2016-10-13 | 2019-01-22 | 中南大学 | A kind of copper carbon composite and preparation method thereof |
| CN108103340B (en) * | 2017-12-21 | 2019-08-06 | 湖北工业大学 | A kind of multistep processes in-situ synthesis of boride titanium-zirconium boride complex phase ceramic enhancing Cu-base composites and its preparation method and application |
| CN108118177A (en) * | 2017-12-21 | 2018-06-05 | 湖北工业大学 | A kind of in-situ synthesis of boride zirconium enhancing Cu-base composites and its preparation method and application |
| CN110512109B (en) * | 2019-09-20 | 2021-09-03 | 西安稀有金属材料研究院有限公司 | Preparation method of graphene reinforced titanium-based composite material |
| CN110670051B (en) * | 2019-09-27 | 2022-04-01 | 郑州大学 | Preparation method of YSZ/Cu ceramic-based metal composite powder suitable for thermal spraying |
| CN115947602B (en) * | 2022-10-10 | 2023-11-07 | 中南大学 | ZrB (ZrB) 2 Metal ceramic-based inert anode and preparation method and application thereof |
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| CN1250108A (en) * | 1999-08-26 | 2000-04-12 | 张曰林 | Ceramic-reinforced copper alloy and its producing process |
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| JPS6256545A (en) * | 1985-09-06 | 1987-03-12 | Asahi Glass Co Ltd | Zrb2-cu type sintered body |
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| CN1250108A (en) * | 1999-08-26 | 2000-04-12 | 张曰林 | Ceramic-reinforced copper alloy and its producing process |
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| Title |
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| Processing and Properties of ZrB2-Cu Composites Sintered by Hot-pressing Sintering;Wei Shang. et al;《Key Engineering Materials》;20140312;第602-603卷;第447-450页 * |
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