CN104911535B - A kind of titanium surface solid boronising boriding medium and boriding process - Google Patents
A kind of titanium surface solid boronising boriding medium and boriding process Download PDFInfo
- Publication number
- CN104911535B CN104911535B CN201510362276.9A CN201510362276A CN104911535B CN 104911535 B CN104911535 B CN 104911535B CN 201510362276 A CN201510362276 A CN 201510362276A CN 104911535 B CN104911535 B CN 104911535B
- Authority
- CN
- China
- Prior art keywords
- boriding
- workpiece
- boronising
- titanium
- boriding medium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Compositions Of Oxide Ceramics (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of titanium surface solid boronising boriding medium and boriding process, boriding medium is made up of 5~93.9wt.% boron sources, 5~25wt.% low-melting compounds, the agent of 1~10wt.% solid oxygen, 0.1~89wt.% diluents.During Bononizing pretreatment, the boriding medium ball milling mixing that will first prepare is uniform, is then charged into boronising tank, simultaneously by titanium metal work-pieces embedment boriding medium, 750~1300 DEG C, after 0.5~24h of insulation are warming up to, workpiece is taken out, is cooled down in a suitable manner, clear up the boriding medium of workpiece surface attachment.Boriding medium of the present invention can improve the speed that boron is migrated to workpiece surface, while boronising rate reduction caused by preventing Titanium base to be oxidized, so as to improve boronising efficiency, be easy to get to thickness is big and uniform infiltration layer, and boronizing process is safe and environment-friendly.
Description
Technical field
The invention belongs to field of metal surface treatment technology, and in particular to a kind of titanium surface solid boronising boriding medium and ooze
Boron technique.
Background technology
Titanium has the advantages that lightweight, intensity corrosion resistance high, good, and its metal material is in many aspects all
Have a wide range of applications, including space flight, military affairs, automobile, medicine equipment, sporting goods, mobile phone etc..However, the wear-resistant energy of titanium
Power is poor, oxidizable under hot conditions and suction hydrogen, causes titanium device performance to be deteriorated even and fails, service life reduction.In recent years, lead to
Crossing the tribological property, high temperature resistant, corrosion resisting property that titanium surface is modified to strengthen titanium becomes the research focus of association area expert.
After the treatment of titanium surface boronizing, the TiB that surface is formed2, TiB have hardness higher, good abrasion resistance, good electric conductivity
And decay resistance.Therefore, boronising is a kind of reinforcing titanium or titanium alloy material surface performance, improves the good of its service life
Method.
Pack boriding method process is simple, flow is short.And, during pack boriding method treatment complex-shaped workpieces, it is also possible to
To diffusion layer organization in uniform thickness.Therefore, it is industrial at present it is most popular be pack boriding method, what is be most widely used is also
The method, other boronizing methods are normally only stagnated in laboratory research.Traditional pack boriding method is typically carried out in solid powder,
The B atoms produced by boron supplying agent in boriding medium need to move to workpiece surface by solid-solid diffusion, and solid-solid diffusion process pole
It is slow, therefore boronising is less efficient.Simultaneously, although inert protective atmosphere can be typically used in boronizing process, but in oxygen
Some metals (such as Ti, Al) can also be oxidized under conditions of pressure is relatively low, hinder B to be spread in matrix.And, it is many during pack boriding
Use KBF4Deng borofluoride as activator, and borofluoride can decompose generation BF in boronising3Etc. the gas of great toxicity
Body, pollutes environment, threatens operator's personal safety, and fluoride has corrosiveness to the workpiece of some materials (such as Ti).Separately
Outward, after conventional method boronising, workpiece surface attachment difficulty is cleaned out, and this may influence the follow-up of workpiece to use.
The present invention is to solve the above problems, it is proposed that a kind of titanium surface solid boronising boriding medium and boriding process, this oozes
The diffusion that boron agent can be B in boriding medium provides liquid channel, accelerates the diffusion of B, and workpiece can be protected not oxidized, improves
Boronising efficiency；The boriding medium not fluoride simultaneously, will not produce the material for having pollution to environment, and boriding medium easily with workpiece point
From.
The content of the invention
It is an object of the invention to be directed to defect present in current pack boriding, there is provided a kind of boronising efficiency high, boronising
Workpiece easy to clean, boronizing process is pollution-free, can obtain big thickness and titanium surface solid boronising boriding medium of uniform infiltration layer and
Boriding process.
The purpose of the present invention is achieved through the following technical solutions.
A kind of titanium surface solid boronising boriding medium, boriding medium is composed of the following components：5~93.9wt.% boron sources, 5~
The solid oxygen agent of 25wt.% low-melting compounds, 1~10wt.%, 0.1~89wt.% diluents, wherein boron source include amorphous boron,
One or more in crystalline boron, ferro-boron, low-melting compound includes B2O3、Na2B4O7、Na2B2O4、K2B4O7、K2B2O4、
Li2B4O7、K2CO3、Na2CO3In one or more, Gu oxygen agent include Al powder, Mg powder in one or two, diluent includes
Al2O3, one or two in MgO.
The preferred proportion scope of boron source is 60~93wt.%, preferably amorphous boron.
The preferred proportion scope of low-melting compound is 5~15wt.%, preferably B2O3、Na2B4O7、Na2B2O4、K2B4O7、
K2CO3、Na2CO3In one or more.
Gu the preferred proportion scope of oxygen agent is 1~6wt.%.
The preferred proportion scope of diluent is 1~25wt.%.
Using the titanium surface solid boriding process of described boriding medium,
(1) boriding medium each component is weighed by proportioning, is well mixed, it is standby；
(2) pretreatment of titanium workpiece surface, standby；
(3) boriding medium after will be well mixed is placed in boronising tank, and workpiece landfill is warmed up into target in boriding medium
Workpiece is taken out in temperature, insulation, cooling, clears up the boriding medium of workpiece surface attachment.
Boriding medium each component dries more than 12h in being previously placed in vacuum drying chamber in step (1)；And mixed using ball milling method
Close uniform, Ball-milling Time is controlled in 2~18h.
The detailed process of titanium workpiece surface pretreatment is in step (2)：Successively with 180#、400#、600#、800#、1000#、
1200#Abrasive paper for metallograph carries out mechanical polishing treatment to surface of workpiece, removes workpiece surface oxide layer and surface is polished,
Workpiece is placed in supersonic wave cleaning machine again cleans 10~30min with acetone, finally rinsed well with deionized water, dried up, treated
With.
Target temperature in step (3) is controlled at 750~1300 DEG C, preferably 950~1200 DEG C；Boronising time control exists
0.5~24h.
Boriding medium of the present invention is not necessarily limited to the surface boronizing treatment of titanium, from suitable low melting point chemical combination
Thing, solid oxygen agent, it can also be used to the Bononizing pretreatment of other metal materials such as Fe, Ni, Mn, Co.
The effect of low-melting compound is to provide liquid phase micro-area in boriding medium of the present invention, is migrations of the B to workpiece surface
Liquid channel is provided, accelerates the dissolving and diffusion of B, improve boronising efficiency.
Solid oxygen agent of the present invention is better than the binding ability of boron, Ti and oxygen with the binding ability of oxygen, and the solid oxygen agent not with
Ti matrixes react.
The effect of diluent of the present invention is the concentration that boron in Reasonable Regulation And Control boriding medium is needed according to boronising.
Boriding medium of the invention can prevent titanium workpiece surface to be oxidized in boronizing process, and boronising efficiency high, boriding medium is easy
Separated with workpiece, and safe and environment-friendly, be readily obtained that thickness is big and the uniform modified boride layer of titanium-based.The present invention is preferably being oozed
Under boron agent component, preferably boronising temperature, preferably boronising time conditions, the bigger boride layer of thickness can be obtained, this can pass through
The contrast of embodiment 1-5 draws.
Brief description of the drawings
Fig. 1 is sample material phase analysis figure in the embodiment of the present invention 1；
Fig. 2 is cross-section morphology figure after sample boronising in the embodiment of the present invention 1.
Specific embodiment
The present invention is intended to further illustrate with reference to embodiments, is not intended to limit the present invention.
Boriding process step of the invention is as follows：
(1) preparation of boriding medium
Each component (be previously placed in vacuum drying chamber and dry more than 12h) is weighed by proportioning, ball milling mixing 2~more than 18h is standby
With；(2) pretreatment of metal surface
Successively with 180#、400#、600#、800#、1000#、1200#Abrasive paper for metallograph is carried out at mechanical polishing to titanium workpiece surface
Reason, removes surface oxide layer, after workpiece is cleaned up with deionized water, then workpiece is placed in acetone is used in supersonic wave cleaning machine
10~30min of cleaning, is finally rinsed well with deionized water, is dried up, stand-by；
(3) Bononizing pretreatment
The boriding medium that will be prepared loads boronising tank, meanwhile, titanium workpiece is filled into boriding medium, it is placed in resistance furnace or electricity frequency
In stove, inert gas is passed through, is warming up to 750~1200 DEG C, after 0.5~24h of insulation, titanium workpiece taken out, it is cold in a suitable manner
But, the electrolyte of cleaning attachment.The inert gas of use include Ar, He in one or two.
Embodiment 1
The boriding medium composition for using is amorphous boron, Na2B4O7, Al powder, Al2O3, specific proportioning is as shown in table 1.
The boriding medium raw material proportioning of 1 embodiment of table 1
| Composition | Amorphous boron | Al powder | ||
| Content (wt.%) | 93 | 5 | 1 | 1 |
(1) preparation of boriding medium
The each component after above-mentioned drying is weighed respectively by proportioning, and ball milling 6h is well mixed, standby.
(2) pretreatment of metal surface
From titanium plate (TA1) as boronising workpiece, titanium plate specification is 40 × 30 × 3mm, successively with 180#、400#、600#、
800#、1000#、1200#Abrasive paper for metallograph carries out mechanical polishing treatment to workpiece, removes surface oxide layer, then workpiece is placed in into ultrasound
20min is cleaned with acetone in ripple cleaning machine, is finally rinsed well with deionized water, dried up, it is stand-by；
(3) Bononizing pretreatment
The boriding medium that will be prepared loads boronising tank, meanwhile, TA1 titanium plates are filled into boriding medium, it is placed in resistance furnace, lead to
Enter Ar as protective atmosphere, be warming up to 900 DEG C, after insulation 2h, titanium workpiece is taken out, cool down in a suitable manner, cleaning attachment
Electrolyte.
XRD detections are carried out to workpiece, its XRD spectrum as shown in figure 1, testing result show workpiece surface infiltration layer by TiB,
TiB2Composition.SEM detections are carried out to workpiece interface, its SEM is schemed as shown in Fig. 2 two-phase boride can be seen in workpiece surface
Layer, outer layer is TiB2Layer, and thickness is homogeneous, this layer of average thickness is 4.87 μm, and secondary outer layer is TiB whiskers layer, and the layer crystal must put down
Equal length is up to 32.87 μm.
Embodiment 2
The boriding medium composition for using is amorphous boron, Na2B4O7, Al powder, Al2O3, specific proportioning is as shown in table 2.
The boriding medium raw material proportioning of 2 embodiment of table 2
| Composition | Amorphous boron | Al powder | ||
| Content (wt.%) | 93 | 5 | 1 | 1 |
(1) preparation of boriding medium
The each component after above-mentioned drying is weighed respectively by proportioning, and ball milling 6h is well mixed, standby.
(2) pretreatment of metal surface
From titanium plate (TA1) as boronising workpiece, titanium plate specification is 40 × 30 × 3mm, successively with 180#、400#、600#、
800#、1000#、1200#Abrasive paper for metallograph carries out mechanical polishing treatment to workpiece, removes surface oxide layer, then workpiece is placed in into ultrasound
20min is cleaned with acetone in ripple cleaning machine, is finally rinsed well with deionized water, dried up, it is stand-by；
(3) Bononizing pretreatment
The boriding medium that will be prepared loads boronising tank, meanwhile, TA1 titanium plates are filled into boriding medium, it is placed in resistance furnace, lead to
Enter Ar as protective atmosphere, be warming up to 950 DEG C, after insulation 2h, titanium workpiece is taken out, cool down in a suitable manner, cleaning attachment
Electrolyte.
Carry out XRD detections to workpiece, the XRD spectrum of workpiece as shown in figure 1, collection of illustrative plates show workpiece surface infiltration layer by TiB,
TiB2Composition, does not find the presence of oxide.SEM detections are carried out to workpiece interface, two-phase boronation can be seen in workpiece surface
Nitride layer, outer layer is TiB2Layer, and thickness is homogeneous, up to 6.76 μm, secondary outer layer is TiB whiskers layer, the layer crystal palpus to this layer of average thickness
Average length is up to 44.78 μm.
Embodiment 3
The boriding medium composition for using is amorphous boron, Na2B4O7, Al powder, Al2O3, specific proportioning is as shown in table 3.
The raw material proportioning of 3 embodiment of table 3
| Composition | Amorphous boron | Al powder | ||
| Content (wt.%) | 65 | 5 | 5 | 25 |
(1) preparation of boriding medium
The each component after above-mentioned drying is weighed respectively by proportioning, and ball milling 6h is well mixed, standby.
(2) pretreatment of metal surface
From titanium plate (TA1) as boronising workpiece, titanium plate specification is 40 × 30 × 3mm, successively with 180#、400#、600#、
800#、1000#、1200#Abrasive paper for metallograph carries out mechanical polishing treatment to workpiece, removes surface oxide layer, then will with deionized water
After workpiece is cleaned up, then workpiece is placed in supersonic wave cleaning machine 20min is cleaned with acetone, it is finally dry with deionized water rinsing
Only, dry up, it is stand-by；
(3) Bononizing pretreatment
The boriding medium that will be prepared loads boronising tank, meanwhile, TA1 titanium plates are filled into boriding medium, it is placed in resistance furnace, lead to
Enter Ar as protective atmosphere, be warming up to 950 DEG C, after insulation 2h, titanium workpiece is taken out, cool down in a suitable manner, cleaning attachment
Electrolyte.
XRD detections are carried out to workpiece, as a result shows workpiece surface infiltration layer by TiB, TiB2Composition, does not find depositing for oxide
.SEM detections are carried out to workpiece interface, two-phase boride layer can be observed in workpiece surface, outer layer is TiB2Layer, and thickness
Homogeneous, this layer of average thickness is 5.19 μm, and secondary outer layer is TiB whiskers layer, and layer crystal palpus average length is up to 37.63 μm.
Embodiment 4
The boriding medium composition for using is amorphous boron, Na2B4O7、K2B4O7, Mg powder, Al2O3, specific proportioning is as shown in table 4.
The raw material proportioning of 4 embodiment of table 4
| Composition | Amorphous boron | Mg powder | |||
| Content (wt.%) | 60 | 5 | 5 | 5 | 25 |
(1) preparation of boriding medium
The each component after above-mentioned drying is weighed respectively by proportioning, and ball milling 12h is well mixed, standby.
(2) pretreatment of metal surface
From titanium plate (TA2) as boronising workpiece, titanium plate specification is 30 × 30 × 4mm, successively with 180#、400#、600#、
800#、1000#、1200#Abrasive paper for metallograph carries out mechanical polishing treatment to workpiece, removes surface oxide layer, then will with deionized water
After workpiece is cleaned up, then workpiece is placed in supersonic wave cleaning machine 15min is cleaned with acetone, it is finally dry with deionized water rinsing
Only, dry up, it is stand-by；
(3) Bononizing pretreatment
The boriding medium that will be prepared loads boronising tank, meanwhile, TA2 titanium plates are filled into boriding medium, it is placed in resistance furnace, lead to
Enter Ar as protective atmosphere, be warming up to 1050 DEG C, after insulation 3h, titanium workpiece is taken out, cool down in a suitable manner, cleaning attachment
Electrolyte.
XRD detections are carried out to workpiece, is found in XRD spectrum it can be seen that obvious TiB, TiB2Characteristic peak, without hair
The presence of existing oxide.SEM detections are carried out to workpiece interface, two-phase boride layer can be observed in workpiece surface, outer layer is
TiB in uniform thickness2Layer, this layer of average thickness is 10.51 μm, and secondary outer layer is the consistent TiB whiskers of orientation, and the layer crystal must be average
Length is up to 49.37 μm.
Embodiment 5
The boriding medium composition for using is amorphous boron, crystallization boron, Na2B4O7、K2B4O7、Na2CO3, Mg powder, MgO, specifically match somebody with somebody
Than as shown in table 5.
The raw material proportioning of 5 embodiment of table 5
| Composition | Amorphous boron | Crystallization boron | Mg powder | MgO | |||
| Content (wt.%) | 40 | 20 | 10 | 10 | 5 | 5 | 10 |
(1) preparation of boriding medium
The each component after above-mentioned drying is weighed respectively by proportioning, and ball milling 8h is well mixed, standby.
(2) pretreatment of metal surface
From titanium plate (TA1) as boronising workpiece, titanium plate dimensions is 30 × 30 × 4mm, successively with 180#、400#、
600#、800#、1000#、1200#Abrasive paper for metallograph carries out mechanical polishing treatment to workpiece, removes surface oxide layer, then spend from
After sub- water cleans up workpiece, then workpiece is placed in supersonic wave cleaning machine cleans 20min with acetone, finally use deionized water
Rinse well, dry up, it is stand-by；
(3) Bononizing pretreatment
The boriding medium that will be prepared loads boronising tank, meanwhile, TA2 titanium plates are filled into boriding medium, it is placed in resistance furnace, lead to
Enter the mixed gas of He and Ar as protective atmosphere, be warming up to 1050 DEG C, after insulation 3h, titanium workpiece is taken out, in a suitable manner
Cooling, clears up the electrolyte of attachment.
XRD detections are carried out to workpiece, TiB, TiB is only detected2Presence.SEM detections, Ke Yi are carried out to workpiece interface
Workpiece surface observes two-phase boride layer, TiB2Thickness degree is 8.74 μm, and TiB whiskers average length is 38.94 μm.
Comparative example 1
Using conventional solid boriding medium boronising, contrasted with the present invention, boriding medium composition is 65wt.%B4C、
35wt.%KBF4。
(1) preparation of boriding medium
The each component after above-mentioned drying is weighed respectively by proportioning, and ball milling 6h is well mixed, standby.
(2) pretreatment of metal surface
From titanium plate (TA2) as boronising workpiece, titanium plate dimensions is 30 × 30 × 4mm, successively with 180#、400#、
600#、800#、1000#、1200#Abrasive paper for metallograph carries out mechanical polishing treatment to workpiece, removes surface oxide layer, then spend from
After sub- water cleans up workpiece, then workpiece is placed in supersonic wave cleaning machine cleans 20min with acetone, finally use deionized water
Rinse well, dry up, it is stand-by；
(3) Bononizing pretreatment
The boriding medium that will be prepared loads boronising tank, meanwhile, TA2 titanium plates are filled into boriding medium, it is placed in resistance furnace, lead to
Enter the mixed gas of He and Ar as protective atmosphere, be warming up to 1050 DEG C, after insulation 3h, titanium workpiece is taken out, in a suitable manner
Cooling, clears up the electrolyte of attachment.
XRD detections are carried out to workpiece, TiB, TiB can be detected2Presence.SEM detections are carried out to workpiece interface, can be with
Two-phase boride layer is observed in workpiece surface, but boride layer thickness is smaller, TiB2Thickness degree is only 4.5 μm, and TiB whiskers are put down
Equal length is only 23 μm, and infiltration layer gross thickness is 27.5 μm, far below institute under same temperature, time conditions in the embodiment of the present invention 4
The alloying layer thickness for obtaining.
Claims (7)
1. a kind of titanium surface solid boronising boriding medium, it is characterised in that boriding medium is composed of the following components：60~93wt.%
The agent of unformed boron, 5~15wt.% low-melting compounds, 1~6wt.% solid oxygen, 1~25wt.% diluents, wherein, low melting point
Compound includes B2O3、Na2B4O7、Na2B2O4、K2B4O7、K2CO3、Na2CO3In one or more, Gu oxygen agent include Al powder, Mg
One or two in powder, diluent includes Al2O3, one or two in MgO.
2. usage right requires the titanium surface solid boriding process of the boriding medium described in 1, it is characterised in that
(1) boriding medium each component is weighed by proportioning, is well mixed, it is standby；
(2) pretreatment of titanium workpiece surface, standby；
(3) boriding medium after will be well mixed is placed in boronising tank, and workpiece landfill is warmed up into target temperature in boriding medium
Workpiece is taken out in degree, insulation, cooling, clears up the boriding medium of workpiece surface attachment.
3. titanium surface solid boriding process according to claim 2, it is characterised in that boriding medium each component in step (1)
It is previously placed in vacuum drying chamber and dries more than 12h；And be well mixed using ball milling method, Ball-milling Time is controlled in 2~18h.
4. titanium surface solid boriding process according to claim 2, it is characterised in that titanium workpiece surface is pre- in step (2)
The detailed process for the treatment of is：Successively with 180#、400#、600#、800#、1000#、1200#Abrasive paper for metallograph enters to surface of workpiece
Row mechanical polishing is processed, and removing workpiece surface oxide layer simultaneously makes surface polish, then workpiece is placed in supersonic wave cleaning machine uses
Acetone cleans 10~30min, is finally rinsed well with deionized water, dries up, stand-by.
5. titanium surface solid boriding process according to claim 2, it is characterised in that the target temperature control in step (3)
System is at 750~1300 DEG C；Boronising time control is in 0.5~24h.
6. titanium surface solid boriding process according to claim 5, it is characterised in that the target temperature control in step (3)
System is at 950~1200 DEG C.
7. the application process of the titanium surface solid boronising boriding medium described in claim 1, it is characterised in that can be used to include
The Bononizing pretreatment of Fe, Ni, Mn, Co in interior metal material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510362276.9A CN104911535B (en) | 2015-06-26 | 2015-06-26 | A kind of titanium surface solid boronising boriding medium and boriding process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510362276.9A CN104911535B (en) | 2015-06-26 | 2015-06-26 | A kind of titanium surface solid boronising boriding medium and boriding process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104911535A CN104911535A (en) | 2015-09-16 |
| CN104911535B true CN104911535B (en) | 2017-06-09 |
Family
ID=54080970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510362276.9A Expired - Fee Related CN104911535B (en) | 2015-06-26 | 2015-06-26 | A kind of titanium surface solid boronising boriding medium and boriding process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104911535B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109182961A (en) * | 2018-10-29 | 2019-01-11 | 山东建筑大学 | A kind of workpiece surface reinforcing low-temperature solid B-Cr-Re reducing agent |
| CN114836711B (en) * | 2022-05-10 | 2023-04-04 | 长沙特耐金属材料科技有限公司 | Metal surface hardening method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3673005A (en) * | 1969-09-18 | 1972-06-27 | Kempten Elektroschmelz Gmbh | Process for borating metals,especially steel |
| US8187393B2 (en) * | 2008-05-28 | 2012-05-29 | Universal Global Products, LLC | Boronization process and composition with improved surface characteristics of metals |
| CN101948997B (en) * | 2010-11-02 | 2012-09-05 | 株洲硬质合金集团有限公司 | Method for surface boriding of hard alloy |
| CN102051572A (en) * | 2011-01-14 | 2011-05-11 | 宝钢集团新疆八一钢铁有限公司 | Surface boronizing treatment method of steel piece |
| CN104451536B (en) * | 2014-12-12 | 2017-02-22 | 西安理工大学 | Method for rapidly boriding Q235 steel |
-
2015
- 2015-06-26 CN CN201510362276.9A patent/CN104911535B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104911535A (en) | 2015-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106835099B (en) | A method of improving stainless steel surface quality | |
| CN102808210A (en) | Micro-arc oxidation surface treatment method and product prepared by same | |
| CN104911535B (en) | A kind of titanium surface solid boronising boriding medium and boriding process | |
| CN105368100B (en) | Coating liquid, coating for the modification of magnetic material surface and preparation method thereof | |
| CN101195913B (en) | Technique for forming chromium carbon nitrogen surface alloying layer by plasma composite process low-temperature | |
| CN101691649B (en) | Titanizing and aluminizing method for sponge titanium reactor | |
| CN103233197A (en) | Low-temperature rapid ion nitriding method of austenitic stainless steel | |
| Lin et al. | Review on improving wear and corrosion resistance of steels via plasma electrolytic saturation technology | |
| CN105908242A (en) | Surface treatment method for magnesium alloy | |
| CN101851736A (en) | Environment-friendly nitrogen-enriched layer rapid nitriding treatment method | |
| CN106756922A (en) | It is a kind of for the black chemical oxidation liquid of steel and its application | |
| CN105154775B (en) | A kind of fusion reactor is used can low temperature generation α-Al2O3The base steel structural material of hydrogen permeation barrier | |
| CN112680090A (en) | Preparation method of corrosion-resistant self-repairing coating on surface of magnesium alloy | |
| CN101693987A (en) | Solution used for quick micro-arc boronisation of mild steel and boronizing method | |
| CN103555104A (en) | High molecular material special for corrosion prevention of steel and iron, and preparation method and application process thereof | |
| CN107513758B (en) | Liquid phase plasma nanometer burnishing liquid, preparation method and the application of one Albatra metal | |
| CN112160001B (en) | Antibacterial, mildewproof and antiviral oxidized stainless steel and preparation method thereof | |
| CN101892468A (en) | Preparation method of chemically plating Ni-W-P ternary alloy on surface of Mg-Li alloy | |
| CN106544657B (en) | Improve coating liquid, the method and its application of material surface modifying layer performance | |
| CN101691648A (en) | Solution for steel quick micro-arc carbonitriding and carbonitriding method | |
| CN108517488B (en) | A kind of alloy material parts surface anticorrosion antiwear composite coating and preparation method thereof | |
| CN107502887A (en) | A kind of processing method for improving Al-alloy products antiseptic property | |
| CN103225058A (en) | High-temperature-oxidation-resistant austenitic stainless steel and preparation method thereof | |
| CN105385988A (en) | Manufacturing method of rare earth metal-boron binary co-penetrated layer on surface of molybdenum or molybdenum alloy | |
| CN1386890A (en) | Dual-layer glow ion carbonizing apparatus and process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170609 Termination date: 20200626 |