CN103866316B - A kind of beryllium material chemical passivation processing method - Google Patents
A kind of beryllium material chemical passivation processing method Download PDFInfo
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- CN103866316B CN103866316B CN201410067851.8A CN201410067851A CN103866316B CN 103866316 B CN103866316 B CN 103866316B CN 201410067851 A CN201410067851 A CN 201410067851A CN 103866316 B CN103866316 B CN 103866316B
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Abstract
The present invention relates to a kind of beryllium material chemical passivation processing method, belong to beryllium material technical field of surface. 1) by the beryllium material surface machine solvent wiping after machining; 2) step 1) is dried up to its surperficial organic solvent with the beryllium material hair-dryer after organic solvent wiping; 3) by step 2) the beryllium material alcoholic solution that obtains carries out ultrasonic cleaning; 4) beryllium material surface chemistry oil removing; 5) the weak etch in beryllium material surface; 6) beryllium material surface passivating treatment: the beryllium material part that weak etch is completed is immersed in passivating dip, carries out Passivation Treatment; Passivation time is 10～20min, and the temperature of passivation operation is 35～45 DEG C. Technique composition of the present invention is simple, workable, can be used for large-scale industrial production.
Description
Technical field
The present invention relates to a kind of beryllium material chemical passivation processing method, belong to beryllium material technical field of surface.
Background technology
Beryllium belongs to very unsettled metal on thermodynamics, exposes and can form one deck as thin as a wafer at ambient temperatureOxide-film, the about 10nm of thickness of this layer of oxide-film. The oxide-film of beryllium is generally made up of two-layer, internal layer oxygenChanging film is the amorphous tight non-porous layer (also claiming barrier layer) near metal surface, and slightly thicker than internal layerLoose outer. Internal layer oxide-film is compressed in beryllium material surface, can form fine and close diaphragm, suppresses slight rottenErosion, so under drying at room temperature atmospheric environment, the corrosion resistance of beryllium material is fine. But beryllium is large humidityCompression ring is easily corroded in border, because its oxide-film is thinner, does not have stronger antiseptic property. ThisTime, the corrosion of beryllium material can be thought the extension of aqueous corrosion, moisture or condensing water vapor in atmosphere provide electrolysisLiquid, causes beryllium and other impurity with oxide-film local defect region to form miniature galvanic cell, and electrification occursLearn corrosion, cause dissolving and the corrosion of metallic beryllium. Meanwhile, beryllium material is microalloy, and on crystal boundary, disperse is distributingBe2C precipitated phase (C content is conventionally 0.15%). Under wet gas environments, Be2C precipitated phase meeting slow reaction,Be transformed into BeO and CH4. Due to Be2C is generally distributed on crystal boundary, Be2C can be oxidized rapidly, makesBeryllium material is along grain boundary corrosion, thus the inefficacy mechanism of triggering beryllium material.
Beryllium material is active metal dust alloy material, and in atmosphere, its surface forms the very thin nature of one deckOxide-film. Under drying at room temperature atmospheric environment, its corrosion resistance is fine, but under moist atmosphere environment, anti-Corrosive nature is poor. In order to meet the requirement of beryllium equipment structure part to Corrosion Protection, need to be to beryllium equipment structure partCarry out surface treatment. Beryllium material surface-treated object is: beryllium material, through preservative treatment, makes its corroding electrode electricityPosition is in BeO passivation region, and the thicker BeO rete of generation one deck, stops chemical attack and the electrification of berylliumLearn the generation of corrosion.
Passivation Treatment is exactly to utilize the chemical reaction between metal surface and chemical mediator solution to generate undissolved nothingMachine salt superficial film, to improve corrosion resistance. Beryllium material chemical passivation processing is the most frequently used process of surface treatment sideMethod, can make beryllium material surface form one deck has the chemical passivation film of anti-corrosion function, improves its decay resistance.About the passivation of beryllium material, data from abroad introduction adopts red fuming nitric acid (RFNA) passivation, after passivation on the surface of beryllium shapeBecome colourless beryllium oxide, its etch resistant properties can improve more than 4 times, but the rete uniformity forming is poor, corrosion resistantDegree of corrosion is inconsistent, and in addition, passivating process adopts large, the general cleaning difficulty of red fuming nitric acid (RFNA) operational dangerTo wash nitric acid residual in part blind hole, this will produce corrosiveness to part, therefore product be adoptedNitric acid passivation is not best method.
Summary of the invention
The object of the invention is in order to overcome the deficiencies in the prior art, propose a kind of beryllium material chemical passivation processing sideMethod, the method, for beryllium material part, meets the needs of product decay resistance, the method technique simple possible,Workable, can be used for beryllium material chemical passivation processing.
The object of the invention is to be achieved through the following technical solutions.
A kind of beryllium material chemical passivation processing method of the present invention, step is:
1) beryllium material surface organic solvent wiping: by the beryllium material piece surface organic solvent wiping after machining,It is conscientiously careful that wiping process needs, and each blind hole on part, screwed hole, groove inside also need careful wipingWipe; The preferred acetone of organic solvent;
2) beryllium material surface hair-dryer dries up: the part that organic solvent wiping is completed, will remain in hair-dryerThe organic solvent on surface dries up, and the temperature that dries up process should be controlled at 35～45 DEG C;
3) ethanolic solution ultrasonic cleaning: the beryllium material part after drying up is immersed in alcoholic solution completely, then existIn supersonic cleaning machine, clean, the frequency of supersonic cleaning machine is 30～40KHz, and the ultrasonic cleaning time is 10～20min,The temperature of alcoholic solution is 35～45 DEG C. Alcoholic solution is to be dissolved in 1000mL by 800～1000mL absolute ethyl alcoholFormulated in deionized water.
4) beryllium material surface chemistry oil removing: the beryllium material part after Ultrasonic Cleaning is immersed in sodium hydroxide solution,Sodium hydroxide solution be dissolved in 1000mL deionized water by 80～100g NaOH formulated, chemistryIn oil removing process, keep 25～35 DEG C of solution temperatures.
5) the weak etch in beryllium material surface: the beryllium material part that oil removing is completed immerses in weak etch solution and carries out weak etchProcess, the etch time is 60～80s, the temperature of etch solution is 25～35 DEG C, weak etch solution be byThe red fuming nitric acid (RFNA) of 600～800mL is dissolved in the deionized water of 200～400mL formulated.
6) beryllium material surface passivating treatment: the beryllium material part that weak etch is completed is immersed in passivating dip, carries outPassivation Treatment. Passivating dip is the mixed liquor of chromium trioxide, the potassium ferricyanide, sodium fluoride and boric acid, by 5～8gThe potassium ferricyanide, 3～5g sodium fluoride and the 1～2mL boric acid of chromium trioxide, 2～5g be dissolved in 1000mL go fromFormulated in sub-water, passivation time is 10～20min, and the temperature of passivation operation is 35～45 DEG C.
Beneficial effect
Technique composition of the present invention is simple, workable, can be used for large-scale industrial production.
Electrochemical deoiling, the thoroughly stain such as greasy dirt, dust on cleaning components surface, makes the passivating film generatingSurface uniform is continuous. Make in follow-up passivating process passivating dip can infiltrate uniformly the table of partFace, the wellability of raising piece surface and passivating dip also strengthens removing in part aperture and deep trouth simultaneouslyOil effect.
Weak etch processing, can remove the natural oxide film of piece surface, and affect hardly piece surfaceRoughness, make beryllium parent metal in the time of Passivation Treatment, can fully contact with chemical passivation solution, canTo improve the quality of beryllium piece surface passivating film, be convenient to generate the passivating film that adhesion is good, quality is high.
Beryllium material chemical passivation processing, for the chemical property of beryllium material, in the mixed liquor of chromic acid and the potassium ferricyanideAdd a small amount of activator, in certain temperature range, metallic beryllium and chromic acid and the potassium ferricyanide react,Generate BeOCr2O3, further forming the very thin inorganic salts rete of one deck on beryllium material surface, this membranous layer ingredient isFor complexity, the main component of general rete is BeOxCr2O3·yCrO3·zH2O。
Brief description of the drawings
Fig. 1 is the 200 times of micrographs of beryllium material passivation test piece in example 1.
Detailed description of the invention
Embodiment 1
In sodium hydroxide solution, carry out electrochemical deoiling, hydroxide by being immersed in through the beryllium material test piece of ultrasonic cleaningSodium solution is to be dissolved in 1000mL deionized water formulatedly by 100g NaOH, in oil removing process, keepsSolution temperature, between 25～30 DEG C, carries out surface chemistry oil removing, oil removing time 5min; Oil removing is completedThe test piece of beryllium material is immersed in weak etch solution carries out weak etch processing, and the weak etch time is 60s, weak etch solutionTemperature be 25 DEG C, weak etch solution is to be dissolved in the deionized water of 400mL and to be joined by the red fuming nitric acid (RFNA) of 600mLSystem forms; The beryllium material part that activation is completed is immersed in passivating dip, carries out Passivation Treatment, and passivation is moltenLiquid is dissolved in 1000mL by the chromium trioxide of 8g, the potassium ferricyanide, 3g sodium fluoride and the commercially available boric acid of 2mL of 5gDeionized water in formulated, passivation time is 10min, the temperature of passivation operation is between 35～45 DEG C.
The beryllium material obtaining is tested as follows:
The outward appearance of passivating film:
Beryllium material part is after chemical passivation is processed, and the surface of its passivating film presents uniform iris to bronzeLook, even film layer is continuous, surface compact, as shown in Figure 1.
Change in size before and after passivation:
Beryllium material is after chemical passivation is processed, and its change in size adopts micrometer to measure, and change in size is-0.001～+ 0.001mm, change in size is less, considers measure error, can think after Passivation TreatmentSize does not change substantially.
Bond strength:
The bond strength of beryllium material chemical passivation film detects, and " QJ479-90 metal-plated coating is in conjunction with strong for normative referenceDegree test method ", adopt cross-hatching and thermal shock method to carry out.
Cross-hatching: adopt blade to draw the grid of 1mm × 1mm on the rete of part, at crosspoint place reteDo not occur peeling, obscission, bond strength is good.
Thermal shock method: part is heated to 220 DEG C and be incubated 30min, puts into immediately cold water after taking-up, changeLearn passivation film and have no peeling, obscission, bond strength is good.
Decay resistance:
The decay resistance of metal surface protection film detects, and conventionally adopts drop experiment. Drop experiment is cleanOn clean sample rete, drip etchant solution, occur that using solution corrosion changes the needed time as anti-corrosionThe judgement of performance and appraisal standards. The corrosion resistance test reference standard QJ471-88 of beryllium material passivating film, selects 3%Copper-bath carries out droplet test, records the time that test piece droplet test reacts. Employing the present invention carryThe beryllium material part of the passivation technology method processing of confession, its corrosion resistance improves 20 times than pure beryllium.
Embodiment 2
Change concentration of sodium hydroxide solution and oil removing time in electrochemical deoiling in embodiment 1, by 80g hydrogen-oxygenChange sodium is dissolved in 1000mL deionized water formulated, and in oil removing process, keeping solution temperature is 25～30 DEG C,Carry out surface chemistry oil removing, oil removing time 3min; All the other conditions are with embodiment 1.
The test piece of gained beryllium material, its passivating film surface presents bronze-colored uniformly, and even film layer is continuous, and surface causesClose, adhesion is good.
Embodiment 3
Change the weak etch time in embodiment 1, the etch time is 80s, and all the other conditions are with embodiment 1.
The test piece of gained beryllium material, its passivating film surface presents bronze-colored uniformly, and even film layer is continuous, and surface causesClose, adhesion is good.
Embodiment 4
Change weak etch solution concentration in embodiment 1, weak etch solution is to be dissolved in by the red fuming nitric acid (RFNA) of 800mLFormulated in the deionized water of 200mL, all the other conditions are with embodiment 1.
The test piece of gained beryllium material, its passivating film surface presents bronze-colored uniformly, and even film layer is continuous, and surface causesClose, adhesion is good.
Embodiment 5
Change passivating dip concentration in embodiment 1, by chromium trioxide, the potassium ferricyanide of 3g, the 5g fluorine of 5gChange in the deionized water that sodium and 1mL boric acid is dissolved in 1000mL formulatedly, all the other conditions are with embodiment 1.
The test piece of gained beryllium material, its passivating film surface presents bronze-colored uniformly, and even film layer is continuous, and surface causesClose, adhesion is good.
Embodiment 6
Change the Passivation Treatment time in embodiment 1, passivation time is 20min, and all the other conditions are with embodiment 5.
The test piece of gained beryllium material, its passivating film surface presents bronze-colored uniformly, and even film layer is continuous, and surface causesClose, adhesion is good.
The present invention not detailed description is known to the skilled person technology.
Claims (4)
1. a beryllium material chemical passivation processing method, is characterized in that step is:
1) by the beryllium material surface machine solvent wiping after machining;
2) by step 1) dry up its surperficial organic solvent with the beryllium material hair-dryer after organic solvent wiping;
3) by step 2) the beryllium material alcoholic solution that obtains carries out ultrasonic cleaning;
4) beryllium material surface chemistry oil removing: the beryllium material part after Ultrasonic Cleaning is immersed in sodium hydroxide solution, keep 25～35 DEG C of solution temperatures in electrochemical deoiling process;
5) the weak etch in beryllium material surface: the beryllium material part that oil removing is completed immerses in weak etch solution and carries out weak etch processing, and the etch time is 60～80s, and the temperature of etch solution is 25～35 DEG C;
6) beryllium material surface passivating treatment: the beryllium material part that weak etch is completed is immersed in passivating dip, carries out Passivation Treatment; Passivation time is 10～20min, and the temperature of passivation operation is 35～45 DEG C;
Step 2) in dry up process temperature be 35～45 DEG C;
Step 3) in ultrasonic cleaning frequency be 30～40KHz, the ultrasonic cleaning time is 10～20min, the temperature of alcoholic solution is 35～45 DEG C, alcoholic solution is the mixture of absolute ethyl alcohol and water, the volume ratio of absolute ethyl alcohol and water is 8～10:10;
Step 6) in passivating dip be the mixed liquor of chromium trioxide, the potassium ferricyanide, sodium fluoride and boric acid, wherein by chromium trioxide: the potassium ferricyanide: sodium fluoride: boric acid: deionized water=5～8g:2～5g:3～5g:1～2mL:1000mL.
2. a kind of beryllium material chemical passivation processing method according to claim 1, is characterized in that: step 1) in organic solvent be acetone.
3. a kind of beryllium material chemical passivation processing method according to claim 1, is characterized in that: step 4) in the concentration of sodium hydroxide solution be 80～100g/L.
4. a kind of beryllium material chemical passivation processing method according to claim 1, is characterized in that: step 5) in weak etch solution the volume ratio of red fuming nitric acid (RFNA) and deionized water be 1.5-4:1.
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| CN107236944A (en) * | 2017-06-19 | 2017-10-10 | 苏州莱特复合材料有限公司 | A kind of preparation method of auto parts powdered-metal passivator |
| CN112974798B (en) * | 2021-02-05 | 2021-11-16 | 哈尔滨工业大学 | Method for dustless treatment of beryllium powder |
| CN113764571B (en) * | 2021-09-07 | 2024-01-23 | 绍兴中芯集成电路制造股份有限公司 | Processing method of substrate with aluminum nitride film layer and preparation method of filter |
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