CN104451731B - Surface oxide layer chemical pickling liquid and application are removed containing Cr and Al elements high temperature alloy - Google Patents

Surface oxide layer chemical pickling liquid and application are removed containing Cr and Al elements high temperature alloy Download PDF

Info

Publication number
CN104451731B
CN104451731B CN201410709388.2A CN201410709388A CN104451731B CN 104451731 B CN104451731 B CN 104451731B CN 201410709388 A CN201410709388 A CN 201410709388A CN 104451731 B CN104451731 B CN 104451731B
Authority
CN
China
Prior art keywords
oxide layer
pickle
temperature alloy
high temperature
pickling
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.)
Active
Application number
CN201410709388.2A
Other languages
Chinese (zh)
Other versions
CN104451731A (en
Inventor
程明
张士宏
叶能永
宋鸿武
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Institute of Metal Research of CAS
Original Assignee
Institute of Metal Research of CAS
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Institute of Metal Research of CAS filed Critical Institute of Metal Research of CAS
Priority to CN201410709388.2A priority Critical patent/CN104451731B/en
Publication of CN104451731A publication Critical patent/CN104451731A/en
Application granted granted Critical
Publication of CN104451731B publication Critical patent/CN104451731B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/10Other heavy metals

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

The present invention relates to a kind of chemical pickling liquid containing Cr and Al elements high temperature alloy removal surface oxide layer and application, belong to the technology field that high temperature alloy chemistry method removes removing oxide layer.The composition of the pickle is:300~400g/L hydrochloric acid, 400~450g/L nitric acid and 100~150g/L hydrogen peroxide, remaining is water.For the high temperature alloy workpiece containing Cr and Al elements in Ni-based, iron-based and cobalt-based, surface oxide layer is removed using the synergy of the hydrochloric acid of certain concentration, nitric acid and hydrogen peroxide, each composition mechanism of action is as follows:Reactant is acted on high-temperature alloy surface oxide based on hydrochloric acid and nitric acid, and hydrogen peroxide accelerates the generation of reaction as catalyst.Substantially, efficiency high, the high-temperature alloy surface after treatment is bright, uniform for pickling effect of the present invention;Pickle of the present invention heat release during proportioning is low, safe without inflammable, sensitization and explosive reactant generation.

Description

Surface oxide layer chemical pickling liquid and application are removed containing Cr and Al elements high temperature alloy
Technical field
The present invention relates to a kind of chemical pickling liquid containing Cr and Al elements high temperature alloy removal surface oxide layer and application, category The technology field of removing oxide layer is gone in high temperature alloy chemistry method.
Background technology
In Ni-based, iron-based and cobalt base superalloy, in order to improve the anti-oxidant and corrosion resistance of alloy, often closing A certain amount of Cr elements are added in gold, the Cr good, fine and close to form adhesiveness2O3Type oxide-film.Meanwhile, the solid solution of alloy and heavy Shallow lake intensified element Ni, Al etc. can also form NiO, Al2O3Oxide-film.Complicated alloying element causes that high temperature alloy oxide-film has The characteristics of multilayer, complex phase, outer layer is with Cr2O3Based on, internal layer is with Al2O3Based on.Although this cause the anti-oxidant of high temperature alloy part and Corrosion resistance is greatly improved, but also to hot forming and heat treatment after, weldment weldering before etc. go removing oxide layer to bring difficulty.Mesh Before, the main removing oxide layer method of going for using has:Embrane method and chemical method are removed in mechanic shot peening method, craft.Although mechanic shot peening method energy Removing oxide layer quickly is removed, but the roughness of alloy surface can be greatly improved simultaneously.For the workpiece with complex profile, because of it It is high to shot-blast process parameter request and substantially reduce its oxide layer removal effect.And using embrane method is gone by hand, be then difficult to Homogenization, the precision of workpiece can also therefore suffer from influence.At present, what industry use was more is chemical method, the pickling for being used Liquid component is:Nitric acid+hydrofluoric acid+water or nitric acid+hydrofluoric acid+sulfuric acid+water etc..Chinese invention patent application (publication number CN103934304A) mention, using nitric acid+hydrofluoric acid+water in mass ratio 0.5:2:7.5 pickles being mixed to get are closed to high temperature Gold treatment.Chinese invention patent application (publication number CN103590057A) is proposed using nitric acid (190g/L-280g/L)+hydrofluoric acid (10g/L-45g/L)+hydrochloric acid (10g/L-45g/L)+hexamethylenetetramine (1g/L-4g/L)+water, in 20 DEG C of -70 DEG C of pickling, place The reason time was at -10 hours 2.5 hours.
In sum, in acid cleaning process, determine that treatment conditions include temperature and time, general effect according to pickling effect Rate is relatively low, relatively costly.Such as when pickle is prepared especially with sulfuric acid, there is highly exothermic danger, use six first Urotropine increases inflammable, sensitization and reactant has volatile danger.
The content of the invention
It is an object of the invention to provide a kind of chemical pickling that surface oxide layer is removed containing Cr and Al elements high temperature alloy Liquid and application, can efficient, inexpensive, low dangerous removal high-temperature alloy surface oxide layer.
The technical scheme is that:
One kind removes surface oxide layer chemical pickling liquid containing Cr and Al elements high temperature alloy, and the composition of the pickle is:300 ~400g/L hydrochloric acid, 400~450g/L nitric acid and 100~150g/L hydrogen peroxide, remaining is water.
Described remove surface oxide layer chemical pickling liquid containing Cr and Al elements high temperature alloy, pickle is preferably constituted For:350g/L hydrochloric acid, 410g/L nitric acid and 130g/L hydrogen peroxide, remaining is water.
The described application that surface oxide layer chemical pickling liquid is removed containing Cr and Al elements high temperature alloy, specific steps are such as Under:
(1) pretreatment of workpiece
It is cleaned by ultrasonic the oil stain and other pollutants of workpiece surface with alcohol or acetone;
(2) pickle is prepared
Using 300~400g/L of concentration hydrochloric acid, 400~450g/L nitric acid and 100~150g/L hydrogen peroxide, remaining is Water, is poured into clean container successively, and pickle minimum volume meets can be completely immersed in workpiece;
(3) control of temperature
To fill in the container immersion thermostat of pickle, thermostat is using water, mixture of ice and water or liquid nitrogen refrigerating agent circulation Cooled down, it is ensured that pickle temperature in acid cleaning process is less than 30 DEG C, it is to avoid vigorous reaction;
(4) acid cleaning process
Under conditions of the change of monitoring pickle temperature at any time, using plastic clamp clamping workpiece, it is put into pickle Continuous vibration washing;
(5) cleaning of workpiece
After pickling terminates, it is cleaned by ultrasonic during workpiece quickly is moved into the container equipped with alcohol or acetone, is washed complete drying .
The described application that surface oxide layer chemical pickling liquid is removed containing Cr and Al elements high temperature alloy, in conditions permit In the case of, process workpiece surface using plastic bruss.
The described application that surface oxide layer chemical pickling liquid is removed containing Cr and Al elements high temperature alloy, container immersion is logical to follow In the thermostat of ring water cooling, it is ensured that pickle temperature in acid cleaning process is preferably 5 DEG C~20 DEG C, vibrated in pickle clear Wash 5~30 minutes.
Advantages of the present invention and beneficial effect are:
1st, substantially, efficiency high, the high-temperature alloy surface after treatment is bright, uniform for pickling effect of the present invention;
2nd, pickle of the present invention heat release during proportioning is low, without inflammable, sensitization and explosive reactant generation, security It is high.
3rd, present invention high temperature alloy workpiece containing Cr and Al elements suitable for Ni-based, iron-based and cobalt-based.
Brief description of the drawings
Fig. 1 is using the test piece schematic diagram after pickling of the present invention.
Specific embodiment
For the high temperature alloy workpiece containing Cr and Al elements in Ni-based, iron-based and cobalt-based, using the hydrochloric acid of certain concentration, nitre The synergy removal surface oxide layer of acid and hydrogen peroxide, each composition mechanism of action is as follows:It is anti-based on hydrochloric acid and nitric acid Ying Tiyu high-temperature alloy surfaces oxide is acted on, and hydrogen peroxide accelerates the generation of reaction as catalyst.
The use process of chemical pickling liquid of the present invention containing Cr and Al elements high temperature alloy removal surface oxide layer is as follows:
(1) pretreatment of workpiece
It is cleaned by ultrasonic the oil stain and other pollutants of workpiece surface with alcohol or acetone.
(2) pickle is prepared
Using 300~400g/L of concentration hydrochloric acid, 400~450g/L nitric acid and 100~150g/L hydrogen peroxide, remaining is Water, pours into clean container successively, as long as pickle minimum volume meets can be completely immersed in workpiece.
(3) control of temperature
To fill in the container immersion thermostat of pickle, thermostat is followed using refrigerants such as water, mixture of ice and water or liquid nitrogen Ring is cooled down, it is ensured that pickle temperature in acid cleaning process is less than 30 DEG C, it is to avoid vigorous reaction.
(4) acid cleaning process
Under conditions of the change of monitoring pickle temperature at any time, using plastic clamp clamping workpiece, it is put into pickle Continuous vibration washing;Workpiece surface can be processed using plastic bruss in the case of conditions permit, accelerate acid cleaning process, further carried Pickling efficiency high.
(5) cleaning of workpiece
After pickling terminates, it is cleaned by ultrasonic during workpiece quickly is moved into the container equipped with alcohol or acetone, is washed complete drying .
Below by embodiment and accompanying drawing, the present invention is described in more detail.
Embodiment
As shown in figure 1, the heat treatment strips of nickel base superalloy IN 718 have oxide layer, the present embodiment is to nickel-base high-temperature Alloy IN 718 is heat-treated the pickling of test piece.
Using plastic clamp, the alloy test pieces of IN 718 after solid solution at 980 DEG C 10 hours are directly placed into dress pickle Pickling is carried out in container.Pickle is constituted:Concentration 350g/L hydrochloric acid, 410g/L nitric acid and 130g/L hydrogen peroxide, remaining is Water.In the thermostat of the logical circulating water of container immersion, it is ensured that pickle temperature in acid cleaning process is less than 30 DEG C (generally 5 DEG C~20 DEG C), vibration washing 10 minutes in pickle.After end, it is 99wt% ethanol quickly to move to equipped with concentration test piece Carry out being cleaned by ultrasonic 3 minutes in solution, wash and finish drying.
As shown in figure 1, compared with original blank, strip oxide layer is removed completely after pickling, and surface-brightening is uniform.
Embodiment result shows, with pickle component in the prior art:" 1. nitric acid+hydrofluoric acid+water, 2. nitric acid+hydrofluoric acid + sulfuric acid+water, 3. nitric acid+hydrofluoric acid+hydrochloric acid+hexamethylenetetramine+water " is compared, using the hydrochloric acid of certain concentration of the present invention, nitre Acid and hydrogen peroxide, hydrogen peroxide accelerate the generation of reaction as catalyst, and its technical characterstic and benefit are:
1st, pickling reaction speed of the present invention is fast, efficiency high;
2nd, substantially, the high-temperature alloy surface after treatment is bright, uniform for pickling effect of the present invention;
3rd, acid cleaning process temperature of the present invention is relatively low and controllable, and working environment is friendly;
4th, pickle of the present invention heat release during proportioning is low, without inflammable, sensitization and explosive reactant generation, security It is high.

Claims (1)

1. a kind of application that surface oxide layer chemical pickling liquid is removed containing Cr and Al elements high temperature alloy, it is characterised in that specific Step is as follows:
The heat treatment strips of nickel base superalloy IN 718 have oxide layer, to the heat treatment test pieces of nickel base superalloy IN 718 Pickling;
Using plastic clamp, the alloy test pieces of IN 718 after solid solution at 980 DEG C 10 hours are directly placed into the container of dress pickle In carry out pickling;Pickle is constituted:Concentration 350g/L hydrochloric acid, 410g/L nitric acid and 130g/L hydrogen peroxide, remaining is water;Hold In the thermostat of the logical circulating water of device immersion, it is ensured that pickle temperature in acid cleaning process is 5 DEG C~20 DEG C, in pickle Vibration washing 10 minutes;After end, test piece is moved to equipped with concentration to carry out being cleaned by ultrasonic 3 minutes in 99wt% ethanol solutions, washed Finish drying;Strip oxide layer is removed completely after pickling, and surface-brightening is uniform.
CN201410709388.2A 2014-11-28 2014-11-28 Surface oxide layer chemical pickling liquid and application are removed containing Cr and Al elements high temperature alloy Active CN104451731B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410709388.2A CN104451731B (en) 2014-11-28 2014-11-28 Surface oxide layer chemical pickling liquid and application are removed containing Cr and Al elements high temperature alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410709388.2A CN104451731B (en) 2014-11-28 2014-11-28 Surface oxide layer chemical pickling liquid and application are removed containing Cr and Al elements high temperature alloy

Publications (2)

Publication Number Publication Date
CN104451731A CN104451731A (en) 2015-03-25
CN104451731B true CN104451731B (en) 2017-06-20

Family

ID=52898461

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410709388.2A Active CN104451731B (en) 2014-11-28 2014-11-28 Surface oxide layer chemical pickling liquid and application are removed containing Cr and Al elements high temperature alloy

Country Status (1)

Country Link
CN (1) CN104451731B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108411315A (en) * 2018-04-17 2018-08-17 贵州振华群英电器有限公司(国营第八九厂) A kind of cleaning technology of TO-5 cases outside and the fifth wheel of inner cavity
CN110670078A (en) * 2019-10-30 2020-01-10 攀钢集团江油长城特殊钢有限公司 Acid pickling method for eliminating GH4099 alloy along crystal oxide layer
CN111139488A (en) * 2020-03-03 2020-05-12 广东富行洗涤剂科技有限公司 Chemical demolding liquid for high-temperature alloy and demolding treatment method thereof
CN112665952B (en) * 2020-10-29 2023-03-24 北京星航机电装备有限公司 GH3128 high-temperature alloy welding seam metallographic structure corrosive agent and corrosion method
CN112962104B (en) * 2021-02-02 2022-12-23 乐普(北京)医疗器械股份有限公司 Method for removing laser processing slag on metal surface and application
CN115261862A (en) * 2022-09-06 2022-11-01 清华大学 Corrosive agent for corroding nickel-based single crystal superalloy, corrosion method and device for realizing method

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103820799A (en) * 2014-03-18 2014-05-28 中冶南方工程技术有限公司 Production method for continuous pickling of hot rolled superaustenitic stainless strip steel

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53117638A (en) * 1977-03-24 1978-10-14 Furukawa Electric Co Ltd:The High speed continuous pickling method for continuous length metal
CN101249444B (en) * 2008-04-14 2011-08-17 长春吉大科诺科技有限责任公司 Method for preparing nitrous oxides selectivity reduction catalyst on metal alloy carrier
CN102443794B (en) * 2011-12-06 2013-07-24 中国科学院金属研究所 Aluminum alloy scratch resistant and fingerprint resistant chromium-free chemical conversion solution for ship and preparation method of conversion film

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103820799A (en) * 2014-03-18 2014-05-28 中冶南方工程技术有限公司 Production method for continuous pickling of hot rolled superaustenitic stainless strip steel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"新型不锈钢氧化皮清除剂的应用";曾德方;《材料保护》;19940131;第27卷(第1期);第39页 *

Also Published As

Publication number Publication date
CN104451731A (en) 2015-03-25

Similar Documents

Publication Publication Date Title
CN104451731B (en) Surface oxide layer chemical pickling liquid and application are removed containing Cr and Al elements high temperature alloy
CN102839364B (en) Surface processing technology of food-grade stainless steel pipe
US4707191A (en) Pickling process for heat-resistant alloy articles
CN105603409A (en) Normal-temperature alkaline chromium-free passivation solution and passivation method for aluminum alloy
CN109136930A (en) The alkaline etching solution of processing method and its use before aluminum alloy surface oxidation
CN106637025A (en) Modified zinc plating treatment process for steel
CN103590057B (en) A kind of acid washing method of aluminium-nickel base contained superalloy
CN107267731A (en) A kind of production technology for automobile exhaust system stainless steel tube
CN108950644A (en) Aluminium alloy anode oxide film remover and method for demoulding
CN105525298A (en) Method for removing titanium and oxide skin on alloy surface of titanium
CN106756975A (en) A kind of surface treatment technique for stainless steel
CN103422051B (en) Remove the method for copper nickel/aluminium graphite compound sealing coating material
CN103966616B (en) A kind of chemical deburring technique for spring surface
CN103789752A (en) Magnesium-alloy nickel-plating solution and nickel-plating method
CN104949570B (en) The cleaning method of boiler
CN105018943B (en) A kind of pickling additive and preparation method thereof
CN106048626A (en) Acid pickling process of stainless steel resistant to salt fog
CN106381499A (en) Acid pickling method of anti-corrosion steel bars
CN101760714A (en) Method for immersion-plating titanium alloy parts
CN104561873B (en) One kind is based on surface preparation carbon steel hot aluminizing technique
JP2012246512A (en) Sealing treatment method for anodic oxide film
CN109536941B (en) AZ31B magnesium alloy golden yellow conversion film treating agent and AZ31B magnesium alloy surface treatment method
CN106238495A (en) spiral wire processing technique
CN105586603B (en) A kind of stainless steel oxidation skin minimizing technology
CN104451722A (en) Method for removing scale on surface of alloy structural steel

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant