CN107385267A - Siluer metal oxide titanium nitride composite electric contact material and preparation method thereof - Google Patents

Siluer metal oxide titanium nitride composite electric contact material and preparation method thereof Download PDF

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Publication number
CN107385267A
CN107385267A CN201710550385.2A CN201710550385A CN107385267A CN 107385267 A CN107385267 A CN 107385267A CN 201710550385 A CN201710550385 A CN 201710550385A CN 107385267 A CN107385267 A CN 107385267A
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powder
oxide
titanium nitride
silver
metal oxide
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缪仁梁
万岱
周克武
姚培建
柏小平
林万焕
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Fuda Alloy Materials Co Ltd
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Fuda Alloy Materials Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C5/00—Alloys based on noble metals
    • C22C5/06—Alloys based on silver
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0005—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with at least one oxide and at least one of carbides, nitrides, borides or silicides as the main non-metallic constituents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H1/00—Contacts
    • H01H1/02—Contacts characterised by the material thereof
    • H01H1/021—Composite material
    • H01H1/023—Composite material having a noble metal as the basic material
    • H01H1/0237—Composite material having a noble metal as the basic material and containing oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
    • H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
    • H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
    • H01H11/048—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts by powder-metallurgical processes

Abstract

The invention provides siluer metal oxide titanium nitride composite electric contact material and preparation method thereof, its technical scheme is that the contact body material includes following components：Metal oxide 1 25%, titanium nitride 0.05 3%, additive≤5%, surplus are silver；The preparation of the contact material includes the production process such as ball milling, mixed powder, compacting, sintering, multiple pressure.Siluer metal oxide titanium nitride composite electric contact material of the present invention has resistance fusion welding good, and contact resistance is low and stably, and preparation method is simple and practical；Contact silver content is reduced simultaneously, certain section silver effect etc. is played, AgMeO contact materials can be substituted in part contactor and breaker.

Description

Siluer metal oxide titanium nitride composite electric contact material and preparation method thereof
Technical field
The invention belongs to Contact Materials for Low Voltage Electric Apparatus field, in particular to siluer metal oxide titanium nitride compound electric to touch Head material and preparation method thereof.
Background technology
At present mostly using silver-based material as electrical contact material in low voltage electrical apparatus industry, and wherein siluer metal oxide （AgMeO, Me refer to metal）Material has excellent anti electric arc corrosion, resistance fusion welding and low and stable contact electricity due to it The comprehensive electrochemical properties of resistance, occupied an important position in whole electrical contact material system.In electrical contact contact process, between contact Melting welding be one of its main failure forms.The common method for improving material resistance fusion welding energy is to improve high-melting-point oxygen in material The content of compound composition, the program can reduce the electric conductivity of material, and the limitation that can be improved.Another kind improves material The method of resistance fusion welding energy makes oxide particle be separated out in needle-like（Needle-like direction is perpendicular to working face）, including this method needs It can just be realized in oxidation technology material, but in powder metallurgic method（Including preoxidation and powder mixing method）But it is difficult real in technique It is existing.
The content of the invention
The invention aims to overcome shortcoming and defect existing for prior art, and it is good to provide a kind of resistance fusion welding, Contact resistance is low and stably, the good siluer metal oxide titanium nitride composite electric contact material of electric conductivity.
Second object of the present invention is to provide a kind of preparation side of siluer metal oxide titanium nitride composite electric contact material Method.
To realize first purpose of the present invention, the technical scheme is that including contact body and silver layer is welded, its Contact body includes following components：Metal oxide 1-25wt%, titanium nitride 0.05-3wt%, additive≤5wt%, surplus are Silver, described additive are nickel oxide, tin oxide, zinc oxide, cupric oxide, bismuth oxide, tungsten oxide, molybdenum oxide, tellurium oxide, oxidation One or more in antimony, indium oxide.
It is to include following components further to set, by percentage to the quality：
CdO 1-25wt%, TiN 0.05-3wt%, additive≤5wt%, surplus are silver,
Wherein additive includes the one or more in following components, in terms of mass fraction：
NiO 0.1-0.5 wt%；SnO20.1-2.0 wt%；ZnO 0.01-2.0 wt%；CuO 0.01-2.0 wt%；Bi2O3 0.01-2.0 wt%；TeO20.01-2.0 wt%；Sb2O30.01-1.0 wt%；In2O3 0.1-1.0 wt%。
It is to include following components further to set, by percentage to the quality：
SnO21-20 wt%, TiN 0.05-3 wt%, the wt% of additive≤5, surplus are silver,
Wherein additive includes the one or more in following components, in terms of mass fraction：
NiO 0.1-0.5 wt%；ZnO 0.01-2.0 wt%；CuO 0.01-2.0 wt%；Bi2O30.01-2.0 wt%；WO3 0.01-2.0 wt%；TeO20.01-2.0 wt%；MoO30.01-2.0 wt%；Sb2O30.01-1.0 wt%；In2O3 0.1- 4.0 wt%。
It is to include following components further to set, by percentage to the quality：
ZnO 1-20wt%, TiN 0.05-3 wt%, the wt% of additive≤5, surplus are silver,
Wherein additive includes the one or more in following components, in terms of mass fraction：
NiO 0.1-0.5 wt%；SnO20.1-2.0 wt%；CuO 0.01-2.0 wt%；Bi2O30.01-2.0 wt%；WO3 0.01-2.0 wt%；TeO20.01-2.0 wt%；MoO30.01-2.0 wt%；Sb2O3 0.01-1.0 wt%。
It is to include following components further to set, by percentage to the quality：
CuO 1-20wt%, TiN 0.05-3 wt%, the wt% of additive≤5, surplus are silver,
Wherein additive includes the one or more in following components, with mass fraction（wt.%）Meter：
NiO 0.1-0.5 wt%；SnO20.1-2.0 wt%；ZnO 0.01-2.0 wt%；Bi2O30.01-2.0 wt%；WO3 0.01-2.0 wt%；TeO20.01-2.0 wt%；MoO30.01-2.0 wt%；Sb2O3 0.01-1.0 wt%。
To realize second goal of the invention of the present invention, its technical scheme is siluer metal oxide titanium nitride composite electric contact material For strip-form contacts material, preparation method includes following process：
（1）Ball milling：Metal oxide powder, nitridation titanium valve, additive powder are put into ball-grinding machine and be pre-mixed uniformly, obtains ball Be milled body, Ball-milling Time 1-10h, wherein, metal oxide：Titanium nitride：The quality parts ratio of additive is：（1-25）： （0.05-3）：（0-5）, described additive is nickel oxide, tin oxide, zinc oxide, cupric oxide, bismuth oxide, tungsten oxide, oxidation One or more in molybdenum, tellurium oxide, antimony oxide, indium oxide；The quality parts ratio of additive is preferably：（1-25）：（0.05- 3）：（0.01-5）
（2）Mixed powder：Ball milling powder and silver powder are put into mixed powder equipment and carry out mixed powder 2-8h, obtains mixed powder；
（3）Compacting：Mixed powder is obtained into first pressing pressed compact using compression-moulding methods, relative density is controlled in 65%-85%；Just In mixed powder solder side side, uniformly one layer of silver powder of paving is controlled in contact gross thickness as welding silver layer, silver thickness during pressure 5%-30%；
（4）Sintering：First pressing pressed compact sinters 2-5h under argon gas or nitrogen protective condition in 600-900 DEG C；
（5）Multiple pressure：Pressed compact after sintering is suppressed into finished product contact in multiple compression mould, multiple pressure pressure 5-15t/cm2。
It is described silver powder granularity 100-300 mesh further to set；Described titanium nitride is added in the form of titanium nitride powder, 0.5-10 μm of particle mean size, using the mixture of one or both of two kinds of nitride two titanium and four nitridation tritanium.
Siluer metal oxide titanium nitride composite electric contact material prepared by the inventive method fully utilizes silver metal oxidation Two kinds of respective advantages of material of thing and titanium nitride, metallographic structure is uniform, every electric property and excellent in mechanical performance, has wider General application.
Titanium nitride fusing point is up to 2950 DEG C, and stability at elevated temperature is good, has good electric conductivity.The present invention uses powder Titanium nitride is uniformly added in AgMeO matrix materials by metallurgy method, and titanium nitride particles will not melt during electrical arc erosion Change, when welding tendency occurs in contact, equally distributed high-melting-point titanium nitride particles, which can play, reduces melting welding power between contact Effect, opens the easy disjunction of contact of melting welding, so as to improve the resistance fusion welding energy of contact.
Further, since the density difference of titanium nitride and silver is larger, and the wetability of titanium nitride powder and silver powder is smaller, therefore The present invention carries out mixed powder preparation using ball milling-blending processes of powders, can by titanium nitride and additive powder by ball milling process Be uniformly mixed in metal oxide powder, then carry out mixed powder again, ensure titanium nitride and the basic Dispersed precipitate of additive in In silver matrix, the program can improve material metallographic structure homogenization degree, be advantageous to improve the combination property of contact material.
The present invention has the advantage that and good effect：1st, titanium nitride is added in AgMeO contact materials, can substantially carried The resistance fusion welding energy of high contact, contact resistance are low and stably, it is possible to increase contactor, the reliability of breaker；2nd, AgMeO is substituted Material, there is certain section silver effect；3rd, powder hybrid technique uses ball milling-blending processes of powders route, can improve material metallographic Microstructure homogenization degree, improve material combination property；4th, the process route that the present invention designs is simple, and stock utilization is high, production Cycle is short, is adapted to produce in enormous quantities.
The present invention is described further with reference to embodiment.
Embodiment
The present invention is specifically described below by embodiment, is served only for that the present invention is further described, no It is understood that for limiting the scope of the present invention, the technician in the field can be according to the content of foregoing invention to the present invention Make some nonessential modifications and adaptations.
Embodiment one：
1) ball milling:3.75kg CdO powder, 0.25kg TiN powder, 0.025kg NiO powder, 0.10kg ZnO powder are put into ball-grinding machine In be pre-mixed uniformly, Ball-milling Time 6h.
2) powder is mixed:4.125kg ball millings powder and 20.875kg Ag powder are put into mixed powder equipment and carry out mixed powder 4h.
3) suppress:Mixed powder is obtained into first pressing pressed compact using compression-moulding methods, relative density is controlled 75%；First pressing When in mixed powder solder side side, uniformly one layer of silver powder of paving is controlled the 15% of contact gross thickness as welding silver layer, silver thickness.
4) sinter:First pressing pressed compact sinters 3h under argon gas protective condition in 700 DEG C.
5) multiple pressure:Pressed compact after sintering is suppressed into Φ 10 × 2mm finished products contact in multiple compression mould, multiple pressure pressure 8t/ cm2。
Embodiment two：
1) ball milling:By 5kg CdO powder, 0.5kg TiN powder, 0.5kg SnO2Powder, 0.125kg CuO powder are put into ball-grinding machine in advance First it is well mixed, Ball-milling Time 8h.
2) powder is mixed:6.125kg ball millings powder and 18.875kg Ag powder are put into mixed powder equipment and carry out mixed powder 8h.
3) suppress:Mixed powder is obtained into first pressing pressed compact using compression-moulding methods, relative density is controlled 75%；First pressing When in mixed powder solder side side, uniformly one layer of silver powder of paving is controlled the 25% of contact gross thickness as welding silver layer, silver thickness.
4) sinter:First pressing pressed compact sinters 5h under nitrogen protective condition in 650 DEG C.
5) multiple pressure:Pressed compact after sintering is suppressed into 15x10x2.5mm finished products contact in multiple compression mould, multiple pressure pressure 10t/cm2。
Embodiment three：
1) ball milling:By 2.0kg SnO2Powder, 0.50kg TiN powder, 0.15kg Bi2O3Powder, 0.10kg WO3Powder is put into ball-grinding machine In be pre-mixed uniformly, Ball-milling Time 3h.
2) powder is mixed:2.75kg ball millings powder and 22.25kg Ag powder are put into mixed powder equipment and carry out mixed powder 3h.
3) suppress:Mixed powder is obtained into first pressing pressed compact using compression-moulding methods, relative density is controlled 65%；First pressing When in mixed powder solder side side, uniformly one layer of silver powder of paving is controlled the 20% of contact gross thickness as welding silver layer, silver thickness.
4) sinter:First pressing pressed compact sinters 4h under argon gas protective condition in 850 DEG C.
5) multiple pressure:Pressed compact after sintering is suppressed into 20x15x2mm finished products contact in multiple compression mould, multiple pressure pressure 12t/ cm2。
Example IV：
1) ball milling:By 3.0kg SnO2Powder, 0.25kg TiN powder, 0.25kg In2O3Powder, 0.25kg Bi2O3Powder and 0.125kg CuO powder, which is put into ball-grinding machine, to be pre-mixed uniformly, Ball-milling Time 5h.
2) powder is mixed:3.875kg ball millings powder and 21.125kg Ag powder are put into mixed powder equipment and carry out mixed powder 6h.
3) suppress:Mixed powder is obtained into first pressing pressed compact using compression-moulding methods, relative density is controlled 80%；First pressing When in mixed powder solder side side, uniformly one layer of silver powder of paving is controlled the 10% of contact gross thickness as welding silver layer, silver thickness.
4) sinter:First pressing pressed compact sinters 3h under nitrogen protective condition in 800 DEG C.
5) multiple pressure:Pressed compact after sintering is suppressed into Φ 20x1.5mm finished products contact in multiple compression mould, multiple pressure pressure 14t/cm2。
Embodiment five：
1) ball milling:By 1.60kg ZnO powder, 0.75kg TiN powder, 0.10kg NiO powder, 0.10kg WO3Powder, 0.05kg TeO2 Powder, which is put into ball-grinding machine, to be pre-mixed uniformly, Ball-milling Time 1h.
2) powder is mixed:2.6kg ball millings powder and 22.40kg Ag powder are put into mixed powder equipment and carry out mixed powder 4h.
3) suppress:Mixed powder is obtained into first pressing pressed compact using compression-moulding methods, relative density is controlled 85%；First pressing When in mixed powder solder side side, uniformly one layer of silver powder of paving is controlled the 10% of contact gross thickness as welding silver layer, silver thickness.
4) sinter:First pressing pressed compact sinters 3h under argon gas protective condition in 800 DEG C.
5) multiple pressure:Pressed compact after sintering is suppressed into 6x4x1mm finished products contact in multiple compression mould, multiple pressure pressure 6t/ cm2。
Embodiment six：
1) ball milling:By 3.75kg ZnO powder, 0.625kg TiN powder, 0.125kg NiO powder, 0.125kg CuO powder, 0.125kg Bi2O3Powder, which is put into ball-grinding machine, to be pre-mixed uniformly, Ball-milling Time 4h.
2) powder is mixed:4.75kg ball millings powder and 20.25kg Ag powder are put into mixed powder equipment and carry out mixed powder 7h.
3) suppress:Mixed powder is obtained into first pressing pressed compact using compression-moulding methods, relative density is controlled 70%；First pressing When in mixed powder solder side side, uniformly one layer of silver powder of paving is controlled the 15% of contact gross thickness as welding silver layer, silver thickness.
4) sinter:First pressing pressed compact sinters 2h under nitrogen protective condition in 900 DEG C.
5) multiple pressure:Pressed compact after sintering is suppressed into Φ 12x2.5mm finished products contact in multiple compression mould, multiple pressure pressure 12t/cm2。
Embodiment seven：
1) ball milling:By 3.75kg CuO powder, 0.5kg TiN powder, 0.05kg NiO powder, 0.05kg MoO3Powder, 0.050kg TeO2 Powder, 0.025kg Sb2O3Powder, 0.025kg ZnO powder, which are put into ball-grinding machine, to be pre-mixed uniformly, Ball-milling Time 10h.
2) powder is mixed:4.45kg ball millings powder and 20.55kg Ag powder are put into mixed powder equipment and carry out mixed powder 6h.
3) suppress:Mixed powder is obtained into first pressing pressed compact using compression-moulding methods, relative density is controlled 65%；First pressing When in mixed powder solder side side, uniformly one layer of silver powder of paving is controlled the 20% of contact gross thickness as welding silver layer, silver thickness.
4) sinter:First pressing pressed compact sinters 5h under argon gas protective condition in 700 DEG C.
5) multiple pressure:Pressed compact after sintering is suppressed into 10x8x1.5mm finished products contact in multiple compression mould, multiple pressure pressure 9t/ cm2。
Embodiment eight：
1) ball milling:By 5.0kg CuO powder, 0.125kg TiN powder, 0.05kg NiO powder, 0.075kg ZnO powder, 0.20kg TeO2 Powder, which is put into ball-grinding machine, to be pre-mixed uniformly, Ball-milling Time 2h.
2) powder is mixed:5.45kg ball millings powder and 19.55kg Ag powder are put into mixed powder equipment and carry out mixed powder 5h.
3) suppress:Mixed powder is obtained into first pressing pressed compact using compression-moulding methods, relative density is controlled 85%；First pressing When in mixed powder solder side side, uniformly one layer of silver powder of paving is controlled the 30% of contact gross thickness as welding silver layer, silver thickness.
4) sinter:First pressing pressed compact sinters 4h under nitrogen protective condition in 750 DEG C.
5) multiple pressure:Pressed compact after sintering is suppressed into Φ 9x1.8mm finished products contact in multiple compression mould, multiple pressure pressure 10t/ cm2。

Claims (7)

  1. A kind of 1. siluer metal oxide titanium nitride composite electric contact material, it is characterised in that：Including contact body and silver layer is welded, Its contact body includes following components：Metal oxide 1-25wt%, titanium nitride 0.05-3wt%, additive≤5wt%, surplus For silver, described additive is nickel oxide, tin oxide, zinc oxide, cupric oxide, bismuth oxide, tungsten oxide, molybdenum oxide, tellurium oxide, oxygen Change the one or more in antimony, indium oxide.
  2. A kind of 2. siluer metal oxide titanium nitride composite electric contact material according to claim 1, it is characterised in that：Including Following components, by percentage to the quality：
    CdO 1-25wt%, TiN 0.05-3wt%, additive≤5wt%, surplus are silver,
    Wherein additive includes the one or more in following components, in terms of mass fraction：
    NiO 0.1-0.5 wt%；SnO20.1-2.0 wt%；ZnO 0.01-2.0 wt%；CuO 0.01-2.0 wt%；Bi2O3 0.01-2.0 wt%；TeO20.01-2.0 wt%；Sb2O30.01-1.0 wt%；In2O3 0.1-1.0 wt%。
  3. A kind of 3. siluer metal oxide titanium nitride composite electric contact material according to claim 1, it is characterised in that：Including Following components, by percentage to the quality：
    SnO21-20 wt%, TiN 0.05-3 wt%, the wt% of additive≤5, surplus are silver,
    Wherein additive includes the one or more in following components, in terms of mass fraction：
    NiO 0.1-0.5 wt%；ZnO 0.01-2.0 wt%；CuO 0.01-2.0 wt%；Bi2O30.01-2.0 wt%；WO3 0.01-2.0 wt%；TeO20.01-2.0 wt%；MoO30.01-2.0 wt%；Sb2O30.01-1.0 wt%；In2O3 0.1- 4.0 wt%。
  4. A kind of 4. siluer metal oxide titanium nitride composite electric contact material according to claim 1, it is characterised in that：Bag Following components is included, by percentage to the quality：
    ZnO 1-20wt%, TiN 0.05-3 wt%, the wt% of additive≤5, surplus are silver,
    Wherein additive includes the one or more in following components, in terms of mass fraction：
    NiO 0.1-0.5 wt%；SnO20.1-2.0 wt%；CuO 0.01-2.0 wt%；Bi2O30.01-2.0 wt%；WO3 0.01-2.0 wt%；TeO20.01-2.0 wt%；MoO30.01-2.0 wt%；Sb2O3 0.01-1.0 wt%。
  5. A kind of 5. siluer metal oxide titanium nitride composite electric contact material according to claim 1, it is characterised in that：Including Following components, by percentage to the quality：
    CuO 1-20wt%, TiN 0.05-3 wt%, the wt% of additive≤5, surplus are silver,
    Wherein additive includes the one or more in following components, with mass fraction（wt.%）Meter：
    NiO 0.1-0.5 wt%；SnO20.1-2.0 wt%；ZnO 0.01-2.0 wt%；Bi2O30.01-2.0 wt%；WO3 0.01-2.0 wt%；TeO20.01-2.0 wt%；MoO30.01-2.0 wt%；Sb2O3 0.01-1.0 wt%。
  6. A kind of 6. preparation method of siluer metal oxide titanium nitride composite electric contact material, it is characterised in that：Siluer metal oxide Titanium nitride composite electric contact material is strip-form contacts material, and preparation method includes following process：
    （1）Ball milling：Metal oxide powder, nitridation titanium valve, additive powder are put into ball-grinding machine and be pre-mixed uniformly, obtains ball Be milled body, Ball-milling Time 1-10h, wherein, metal oxide：Titanium nitride：The quality parts ratio of additive is：（1-25）： （0.05-3）：（0-5）, described additive is nickel oxide, tin oxide, zinc oxide, cupric oxide, bismuth oxide, tungsten oxide, oxidation One or more in molybdenum, tellurium oxide, antimony oxide, indium oxide；
    （2）Mixed powder：Ball milling powder and silver powder are put into mixed powder equipment and carry out mixed powder 2-8h, obtains mixed powder；
    （3）Compacting：Mixed powder is obtained into first pressing pressed compact using compression-moulding methods, relative density is controlled in 65%-85%；Just In mixed powder solder side side, uniformly one layer of silver powder of paving is controlled in contact gross thickness as welding silver layer, silver thickness during pressure 5%-30%；
    （4）Sintering：First pressing pressed compact sinters 2-5h under argon gas or nitrogen protective condition in 600-900 DEG C；
    （5）Multiple pressure：Pressed compact after sintering is suppressed into finished product contact in multiple compression mould, multiple pressure pressure 5-15t/cm2。
  7. 7. a kind of preparation method of siluer metal oxide titanium nitride composite electric contact material according to claim 6, it is special Sign is：Described silver powder granularity 100-300 mesh；Described titanium nitride is added in the form of titanium nitride powder, particle mean size 0.5- 10 μm, using the mixture of one or both of two kinds of nitride two titanium and four nitridation tritanium.
CN201710550385.2A 2017-07-07 2017-07-07 Siluer metal oxide titanium nitride composite electric contact material and preparation method thereof Pending CN107385267A (en)

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CN105200262A (en) * 2015-09-23 2015-12-30 福达合金材料股份有限公司 Preparation method of silver-based flaky electric contact material high in stannic oxide content

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117107100A (en) * 2023-08-28 2023-11-24 昆明理工大学 Method for reinforcing silver-based material by metal oxide with core-shell structure
CN117107100B (en) * 2023-08-28 2024-01-30 昆明理工大学 Method for reinforcing silver-based material by metal oxide with core-shell structure

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