阅读说明：本技术 镍磷中间合金及其制备方法与应用 (Nickel-phosphorus intermediate alloy and preparation method and application thereof ) 是由 王蕾 于 2021-08-03 设计创作，主要内容包括：本发明公开了一种镍磷中间合金及其制备方法与应用。所述制备方法包括：提供金属镍和镍磷合金；将部分的所述金属镍与镍磷合金于900℃以上热处理5～60min,之后加入余量的金属镍,并于1000～1100℃熔炼1～20min,获得第一熔融金属液；将液态白磷注入所述第一熔融金属液中,并于1000℃以上热处理1～10min,获得镍磷中间合金。本发明采用白磷作为磷源,减少了镍磷合金中杂质的引入,同时本发明的熔炼温度较低,实现了低能耗、低污染、低碳排放的镍磷加工。(The invention discloses a nickel-phosphorus intermediate alloy and a preparation method and application thereof. The preparation method comprises the following steps: providing metallic nickel and nickel-phosphorus alloy; heat-treating part of the metal nickel and the nickel-phosphorus alloy at the temperature of over 900 ℃ for 5-60 min, then adding the rest metal nickel, and smelting at the temperature of 1000-1100 ℃ for 1-20 min to obtain a first molten metal; and injecting liquid white phosphorus into the first molten metal liquid, and carrying out heat treatment at the temperature of more than 1000 ℃ for 1-10 min to obtain the nickel-phosphorus intermediate alloy. The invention adopts white phosphorus as a phosphorus source, reduces the introduction of impurities in the nickel-phosphorus alloy, has lower smelting temperature, and realizes the nickel-phosphorus processing with low energy consumption, low pollution and low carbon emission.)

1. A preparation method of a nickel-phosphorus intermediate alloy is characterized by comprising the following steps:

providing metallic nickel and nickel-phosphorus alloy;

heat-treating part of the metal nickel and the nickel-phosphorus alloy at the temperature of over 900 ℃ for 5-60 min, then adding the rest metal nickel, and smelting at the temperature of 1000-1100 ℃ for 1-20 min to obtain a first molten metal;

and injecting liquid white phosphorus into the first molten metal liquid, and carrying out heat treatment at the temperature of more than 1000 ℃ for 1-10 min to obtain the nickel-phosphorus intermediate alloy.

2. The method according to claim 1, comprising:

placing part of the metal nickel and the nickel-phosphorus alloy in a heating device, heating the heating device to 600 ℃ at a heating rate of 10-30 ℃/min, heating to 900-950 ℃ at a heating rate of 5-15 ℃/min for heat treatment, adding the rest of metal nickel, heating to 1000-1100 ℃ and carrying out smelting treatment to obtain the first molten metal;

and/or the preparation method specifically comprises the following steps: injecting liquid white phosphorus into the first molten metal liquid at the temperature of 1000-1100 ℃ and carrying out heat treatment to obtain the nickel-phosphorus intermediate alloy; preferably, a graphite phosphorus injection device is used to inject liquid white phosphorus into the first molten metal.

3. The method of claim 1, wherein: the mass ratio of the metal nickel to the nickel-phosphorus alloy is 90-99: 1-10;

and/or the mass ratio of the metal nickel to the liquid white phosphorus is 75-95: 5-25;

and/or, the metallic nickel comprises an electrolytic nickel plate.

4. A nickel phosphorous master alloy prepared by the method of any one of claims 1 to 3.

5. Use of the nickel phosphorous master alloy of claim 4 for the preparation of a nickel phosphorous alloy or a nickel based brazing material.

6. A preparation method of a nickel-phosphorus alloy is characterized by comprising the following steps:

providing metallic nickel;

preparing a nickel phosphorus master alloy by the method of any one of claims 1 to 3;

carrying out heat treatment on the nickel-phosphorus intermediate alloy and part of the metal nickel at 900-950 ℃, then adding the rest metal nickel, and carrying out smelting treatment at 1000-1100 ℃ to obtain a second molten metal solution;

and injecting liquid white phosphorus into the second molten metal liquid, and carrying out heat treatment at the temperature of more than 1000 ℃ for 1-10 min to obtain the nickel-phosphorus alloy.

7. The method according to claim 6, comprising:

placing the nickel-phosphorus intermediate alloy and part of the metal nickel in a heating device, heating the heating device to 600 ℃ at a heating rate of 10-30 ℃/min, heating to over 900 ℃ at a heating rate of 5-15 ℃/min, carrying out heat treatment for 5-60 min, adding the rest of metal nickel, heating to 1000-1100 ℃, and carrying out smelting treatment for 1-20 min to obtain a second molten metal;

and/or the preparation method specifically comprises the following steps: injecting liquid white phosphorus into the second molten metal liquid at the temperature of 1000-1100 ℃ for heat treatment for 1-10 min to obtain the nickel-phosphorus alloy; preferably, a graphite phosphorus injection device is used to inject liquid white phosphorus into the second molten metal.

8. The method of claim 1, wherein: the mass ratio of the metal nickel to the nickel-phosphorus intermediate alloy is 90-99: 1-10;

and/or the mass ratio of the metal nickel to the liquid white phosphorus is 75-95: 5-25;

and/or, the metallic nickel comprises an electrolytic nickel plate.

9. A nickel phosphorous alloy produced by the method of any one of claims 6 to 8.

10. A nickel-based brazing material characterized by comprising the nickel-phosphorus master alloy of claim 5 or the nickel-phosphorus alloy of claim 9.

Technical Field

The invention belongs to the technical field of metal alloys, and particularly relates to a nickel-phosphorus intermediate alloy and a preparation method and application thereof.

Background

With the popularization and use of stainless steel in automobile parts, oil and gas pipelines, radiators and exchangers. The brazing process of stainless steel parts also faces new technological changes. The traditional copper-based brazing material needs high brazing temperature, and meanwhile, the welding strength of a brazing part and the corrosion resistance of a part are required to be improved. A novel nickel-based brazing material, which is obtained by adding elements such as chromium, iron, boron, phosphorus, silicon and the like to nickel, has a lower brazing temperature. And the phosphorus element in the nickel-based brazing material is mainly added in the form of nickel-phosphorus alloy.

In the prior art, more copper-phosphorus alloy preparation technologies are provided, the processing and manufacturing processes related to nickel-phosphorus alloys are less, and the demand of the market on the nickel-phosphorus alloys is continuously increased along with the development of stainless steel brazing technologies. The prior preparation process method of the nickel-phosphorus intermediate alloy mainly adopts a phosphorus pressing method, namely red phosphorus is used as a phosphorus source, the red phosphorus is firstly placed in a crucible, an isolation material layer made of quartz sand and the like is placed on the red phosphorus, then a nickel plate and other metal raw materials are placed in the crucible, the temperature is raised to be higher than the melting point temperature of the metal raw materials for heat preservation, after the metal raw materials are completely melted, the isolation layer is broken to ensure that the red phosphorus enters molten metal, and the isolation layer material in the molten metal is removed, so that the nickel-phosphorus alloy is obtained; impurities are introduced into the isolating layer material used in the method, and meanwhile, the melting of the metal raw material needs higher temperature and higher energy consumption, so that the development of a low-temperature, quick, green, environment-friendly and efficient nickel-phosphorus intermediate alloy processing technology is urgently needed.

Disclosure of Invention

The invention mainly aims to provide a nickel-phosphorus intermediate alloy, a preparation method and application thereof, so as to overcome the defects of the prior art.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

the embodiment of the invention provides a preparation method of a nickel-phosphorus intermediate alloy, which comprises the following steps:

providing metallic nickel and nickel-phosphorus alloy;

heat-treating part of the metal nickel and the nickel-phosphorus alloy at the temperature of over 900 ℃ for 5-60 min, then adding the rest metal nickel, and smelting at the temperature of 1000-1100 ℃ for 1-20 min to obtain a first molten metal;

and injecting liquid white phosphorus into the first molten metal liquid, and carrying out heat treatment at the temperature of more than 1000 ℃ for 1-10 min to obtain the nickel-phosphorus intermediate alloy.

The embodiment of the invention also provides the nickel-phosphorus master alloy prepared by the method.

The embodiment of the invention also provides the application of the nickel-phosphorus master alloy in preparing a nickel-phosphorus alloy or a nickel-based brazing material.

The embodiment of the invention also provides a preparation method of the nickel-phosphorus alloy, which comprises the following steps:

providing metallic nickel;

preparing a nickel-phosphorus intermediate alloy by adopting the method;

carrying out heat treatment on the nickel-phosphorus intermediate alloy and part of the metal nickel at the temperature of over 900 ℃, then adding the rest of the metal nickel, and carrying out smelting treatment at the temperature of 1000-1100 ℃ to obtain a second molten metal solution;

and injecting liquid white phosphorus into the second molten metal liquid, and carrying out heat treatment at the temperature of more than 1000 ℃ for 1-10 min to obtain the nickel-phosphorus alloy.

The embodiment of the invention also provides the nickel-phosphorus alloy prepared by the method.

The embodiment of the invention also provides a nickel-based brazing material which comprises the nickel-phosphorus intermediate alloy or the nickel-phosphorus alloy.

Compared with the prior art, the invention has the beneficial effects that:

(1) according to the invention, white phosphorus is used as a phosphorus source (the white phosphorus is in a liquid state at the temperature of more than 40 ℃), and the liquid phosphorus is directly injected into molten nickel by using the phosphorus injector, so that the use of quartz sand and other isolation materials in a phosphorus pressing method is effectively avoided, and the introduction of impurities in the nickel-phosphorus alloy is reduced;

(2) in the nickel smelting process, a small amount of nickel-phosphorus alloy (Ni is known from a Ni-P binary phase diagram) is added into a nickel plate₃The melting point of P is 880 ℃), the melting temperature of the nickel plate can be reduced, the melting efficiency is improved, and the nickel can be rapidly melted (the conventional melting temperature of the nickel plate is more than 1200 ℃) in the lower temperature range of 1000-1100 ℃, so that the nickel-phosphorus processing and synthesis with low energy consumption, low pollution and low carbon emission can be realized.

Detailed Description

The present invention provides a processing and manufacturing process of nickel-phosphorus alloy, which is low-temperature, fast, green, environment-friendly and efficient, and aims to overcome the defects of high energy consumption and high carbon emission caused by adopting a higher heating and melting temperature and a longer heating and melting time in the conventional processing technology of phosphorus master alloy.

The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. 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.

One aspect of an embodiment of the present invention provides a method for preparing a nickel-phosphorus master alloy, including:

providing metallic nickel and nickel-phosphorus alloy;

heat-treating part of the metal nickel and the nickel-phosphorus alloy at the temperature of over 900 ℃ for 5-60 min, then adding the rest metal nickel, and smelting at the temperature of 1000-1100 ℃ for 1-20 min to obtain a first molten metal;

and injecting liquid white phosphorus into the first molten metal liquid, and carrying out heat treatment at the temperature of more than 1000 ℃ for 1-10 min to obtain the nickel-phosphorus intermediate alloy.

In some more specific embodiments, the preparation method specifically comprises: and (2) placing part of the metal nickel and the nickel-phosphorus alloy in a heating device, heating the heating device to 600 ℃ at a heating rate of 10-30 ℃/min, heating to over 900 ℃ at a heating rate of 5-15 ℃/min for heat treatment, adding the rest of metal nickel, heating to 1000-1100 ℃ and carrying out smelting treatment to obtain the first molten metal.

In some more specific embodiments, the preparation method specifically comprises: and injecting liquid white phosphorus into the first molten metal liquid at the temperature of 1000-1100 ℃ and carrying out heat treatment to obtain the nickel-phosphorus intermediate alloy.

Further, a graphite phosphorus injection device (graphite phosphorus injection pipe) is adopted to inject liquid white phosphorus into the first molten metal liquid.

In some specific embodiments, the mass ratio of the metallic nickel to the nickel-phosphorus alloy is 90-99: 1-10.

Furthermore, the mass ratio of the metal nickel to the liquid white phosphorus is 75-95: 5-25.

Further, the metallic nickel includes an electrolytic nickel plate, and is not limited thereto.

In some more specific embodiments, the method of preparing the nickel-phosphorus master alloy may include:

(1) weighing an electrolytic nickel plate and a nickel-phosphorus alloy according to the percentage of the materials;

(2) putting the nickel-phosphorus alloy and half of the electrolytic nickel plate into a melting crucible, starting to heat up, and heating the furnace body to 600 ℃ at the heating rate of 1-30 ℃/min;

(3) raising the temperature to over 900 ℃ at the speed of 5-15 ℃/min for heat preservation; under the action of the nickel-phosphorus alloy, the nickel plate starts to melt; after adding the rest nickel plate, heating the furnace to 1000-1100 ℃ for heat preservation and smelting until the nickel plate is completely melted;

(4) keeping the temperature of the furnace body at 1000-1100 ℃, enabling a graphite phosphorus injection pipe to go deep under molten metal, and injecting liquid white phosphorus according to the percentage of materials;

(5) after stopping injecting phosphorus, continuously keeping the furnace temperature at about 1000 ℃ for 10 min; and then cooling to obtain the nickel-phosphorus intermediate alloy.

(6) Leaving a proper nickel-phosphorus intermediate alloy as a raw material to be continuously used.

Another aspect of an embodiment of the present invention also provides a nickel-phosphorus master alloy prepared by the foregoing method.

In a further aspect of embodiments of the present invention there is also provided the use of a nickel phosphorous master alloy as hereinbefore described for the preparation of a nickel phosphorous alloy or a nickel based brazing material.

Another aspect of an embodiment of the present invention also provides a method for preparing a nickel-phosphorus alloy, including:

providing metallic nickel;

preparing a nickel-phosphorus intermediate alloy by adopting the method;

adding the nickel phosphorus intoPerforming heat treatment on the master alloy and part of the metal nickel at the temperature of more than 900 ℃, adding the rest of the metal nickel, and performing smelting treatment at the temperature of 1000-1100 ℃ to obtain the nickel-nickel alloySecond molten metal；

And injecting liquid white phosphorus into the second molten metal liquid, and carrying out heat treatment at the temperature of more than 1000 ℃ for 1-10 min to obtain the nickel-phosphorus alloy.

In some more specific embodiments, the preparation method specifically comprises: and placing the nickel-phosphorus intermediate alloy and part of the metal nickel in a heating device, heating the heating device to 600 ℃ at a heating rate of 10-30 ℃/min, heating to over 900 ℃ at a heating rate of 5-15 ℃/min, carrying out heat treatment for 5-60 min, adding the rest of metal nickel, heating to 1000-1100 ℃, and carrying out smelting treatment for 1-20 min to obtain the second molten metal liquid.

In some more specific embodiments, the preparation method specifically comprises: injecting liquid white phosphorus into the second molten metal liquid at the temperature of 1000-1100 ℃ for heat treatment for 1-10 min to obtain the nickel-phosphorus alloy; preferably, a graphite phosphorus injection device is used to inject liquid white phosphorus into the second molten metal.

In some specific embodiments, the mass ratio of the metallic nickel to the nickel-phosphorus master alloy is 90-99: 1-10.

Furthermore, the mass ratio of the metal nickel to the liquid white phosphorus is 75-95: 5-25.

Further, the metallic nickel includes an electrolytic nickel plate, and is not limited thereto.

Another aspect of an embodiment of the present invention also provides a nickel-phosphorus alloy prepared by the foregoing method.

In another aspect of the embodiments of the present invention, there is also provided a nickel-based brazing material including the aforementioned nickel-phosphorus master alloy or nickel-phosphorus alloy.

The nickel-based brazing material in the present invention is formed by adding the aforementioned nickel-phosphorus master alloy or nickel-phosphorus alloy to metallic nickel.

The technical solution of the present invention is further described in detail with reference to several preferred embodiments, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following embodiments.

The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.

Example 1: preparation of nickel-phosphorus master alloy

(1) Weighing 52 kg of electrolytic nickel plate and 30 kg of nickel-phosphorus alloy;

(2) putting the nickel-phosphorus alloy and a half of the electrolytic nickel plate into a melting crucible, starting to heat up, and heating the furnace body to 600 ℃ at the heating rate of 20 ℃/min;

(3) heating to 950 ℃ at the speed of 10 ℃/min and preserving heat; at the moment, the nickel-phosphorus alloy begins to melt; after 15min, adding the rest nickel plates, heating the furnace to 1050 ℃ for heat preservation smelting until the nickel plates are completely melted;

(4) keeping the furnace temperature at 1050 ℃, putting a graphite phosphorus injection pipe into the molten metal, and injecting white phosphorus solution according to the mass percentage;

(5) after stopping injecting phosphorus, continuously keeping the furnace temperature at 1000 ℃ for 10 min; and then cooling to obtain the nickel-phosphorus intermediate alloy.

Example 2: preparation of nickel-phosphorus master alloy

(1) Weighing 200 kg of electrolytic nickel plate and 50 kg of nickel-phosphorus alloy;

(2) putting the nickel-phosphorus alloy and a half of the electrolytic nickel plate into a melting crucible, starting to heat up, and heating the furnace body to 600 ℃ at the heating rate of 25 ℃/min;

(3) heating to 980 ℃ at the speed of 10 ℃/min for heat preservation, and melting the nickel-phosphorus alloy; after 15min, adding the rest nickel plates, heating the furnace to 1100 ℃ for heat preservation and smelting until the nickel plates are completely melted;

(4) keeping the furnace temperature at 1100 ℃, putting a graphite phosphorus injection pipe into the molten metal, and injecting white phosphorus solution according to the mass percentage;

(5) after stopping injecting phosphorus, continuously keeping the furnace temperature at 1050 ℃ for 10 min; and then cooling to obtain the nickel-phosphorus intermediate alloy.

Example 3: preparation of nickel-phosphorus master alloy

(1) Weighing 100 kg of electrolytic nickel plate and 30 kg of nickel-phosphorus alloy;

(2) putting the nickel-phosphorus alloy and a half of the electrolytic nickel plate into a melting crucible, starting to heat up, and heating the furnace body to 600 ℃ at the heating rate of 15 ℃/min;

(3) heating to 900 deg.C at a speed of 10 deg.C/min for heat preservation; at the moment, the nickel-phosphorus alloy begins to melt; after 15min, adding the rest nickel plates, heating the furnace to 1010 ℃, and carrying out heat preservation smelting until the nickel plates are completely melted;

(4) keeping the furnace temperature at 1010 ℃, putting a graphite phosphorus injection pipe into the molten metal liquid, and injecting white phosphorus solution according to the mass percentage;

(5) after stopping injecting phosphorus, continuously keeping the furnace temperature at 1000 ℃ for 10 min; and then cooling to obtain the nickel-phosphorus alloy.

Example 4: preparation of nickel-phosphorus master alloy

(1) Weighing 99 kg of electrolytic nickel plate and 1 kg of nickel-phosphorus alloy;

(2) putting the nickel-phosphorus alloy and half of the electrolytic nickel plate into a melting crucible, starting to heat up, and heating the furnace body to 600 ℃ at the heating rate of 10 ℃/min;

(3) heating to 900 ℃ at the speed of 5 ℃/min for heat preservation, melting the nickel-phosphorus alloy, adding the rest nickel plate after 60min, heating the furnace to 1000 ℃ for heat preservation and melting for 20min until the nickel plate is completely melted;

(4) keeping the furnace temperature at 1000 ℃, putting a graphite phosphorus injection pipe into the molten metal liquid, and injecting white phosphorus solution according to the mass percentage (the mass ratio of the nickel plate to the liquid white phosphorus is 19: 1);

(5) after stopping injecting phosphorus, continuously keeping the furnace temperature at 1000 ℃ for 10 min; and then cooling to obtain the nickel-phosphorus alloy.

Example 5: preparation of nickel-phosphorus master alloy

(1) Weighing 90 kg of electrolytic nickel plate and 10 kg of nickel-phosphorus alloy;

(2) putting the nickel-phosphorus alloy and a half of the electrolytic nickel plate into a melting crucible, starting to heat up, and heating the furnace body to 600 ℃ at the heating rate of 30 ℃/min;

(3) heating to 950 ℃ at the speed of 15 ℃/min for heat preservation, melting the nickel-phosphorus alloy, adding the rest nickel plate after 5min, heating the furnace to 1100 ℃ for heat preservation and melting for 1min until the nickel plate is completely melted;

(4) keeping the furnace temperature at 1100 ℃, putting a graphite phosphorus injection pipe into the molten metal liquid, and injecting white phosphorus solution according to the mass percentage (the mass ratio of the nickel plate to the liquid white phosphorus is 3: 1);

(5) after stopping injecting phosphorus, continuously keeping the furnace temperature at 1100 ℃ for 10 min; and then cooling to obtain the nickel-phosphorus alloy.

Example 6: preparation of nickel-phosphorus alloy

(1) Weighing 52 kg of electrolytic nickel plate and 30 kg of the nickel-phosphorus master alloy prepared in the example 1;

(2) putting the nickel-phosphorus intermediate alloy and a half of the electrolytic nickel plate into a melting crucible, starting to heat up, and heating the furnace body to 600 ℃ at the heating rate of 20 ℃/min;

(3) heating to 950 ℃ at the speed of 10 ℃/min for heat preservation, melting the nickel-phosphorus alloy, adding the rest nickel plate after 30min, heating the furnace to 1050 ℃ for heat preservation melting for 10min until the nickel plate is completely melted;

(4) keeping the furnace temperature at 1050 ℃, putting a graphite phosphorus injection pipe into the molten metal liquid, and injecting white phosphorus solution according to the mass percentage (the mass ratio of the nickel plate to the liquid white phosphorus is 80: 10);

(5) after stopping injecting phosphorus, continuously keeping the furnace temperature at 1000 ℃ for 5 min; and then cooling to obtain the nickel-phosphorus alloy.

Example 7: preparation of nickel-phosphorus alloy

(1) 198 kg of electrolytic nickel plate and 2 kg of the nickel-phosphorus master alloy prepared in the example 1 are weighed;

(2) putting the nickel-phosphorus intermediate alloy and a half of the electrolytic nickel plate into a melting crucible, starting to heat up, and heating the furnace body to 600 ℃ at the heating rate of 10 ℃/min;

(3) heating to 900 ℃ at the speed of 5 ℃/min for heat preservation, melting the nickel-phosphorus alloy, adding the rest nickel plate after 60min, heating the furnace to 1000 ℃ for heat preservation and melting for 20min until the nickel plate is completely melted;

(4) keeping the furnace temperature at 1000 ℃, putting a graphite phosphorus injection pipe into the molten metal liquid, and injecting white phosphorus solution according to the mass percentage (the mass ratio of the nickel plate to the liquid white phosphorus is 95: 5);

(5) and after stopping injecting phosphorus, continuously keeping the furnace temperature at 1000 ℃ for 10min, and then cooling to obtain the nickel-phosphorus alloy.

Example 8: preparation of nickel-phosphorus alloy

(1) Weighing 90 kg of electrolytic nickel plate and 10 kg of nickel-phosphorus master alloy prepared in example 1;

(2) putting the nickel-phosphorus intermediate alloy and a half of the electrolytic nickel plate into a melting crucible, starting to heat up, and heating the furnace body to 600 ℃ at the heating rate of 30 ℃/min;

(3) heating to 950 ℃ at the speed of 15 ℃/min for heat preservation, melting the nickel-phosphorus alloy, adding the rest nickel plate after 5min, heating the furnace to 1100 ℃ for heat preservation and melting for 1min until the nickel plate is completely melted;

(4) keeping the furnace temperature at 1100 ℃, putting a graphite phosphorus injection pipe into the molten metal liquid, and injecting white phosphorus solution according to the mass percentage (the mass ratio of the nickel plate to the liquid white phosphorus is 75: 25);

(5) after stopping injecting phosphorus, continuously keeping the furnace temperature at 1000 ℃ for 1 min; and then cooling to obtain the nickel-phosphorus alloy.

In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.

It should be understood that the technical solution of the present invention is not limited to the above-mentioned specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention without departing from the spirit of the present invention and the protection scope of the claims.