CN109632916A - A method of measurement increasing material manufacturing titanium alloy surface Stability of Passive Film - Google Patents
A method of measurement increasing material manufacturing titanium alloy surface Stability of Passive Film Download PDFInfo
- Publication number
- CN109632916A CN109632916A CN201811564438.7A CN201811564438A CN109632916A CN 109632916 A CN109632916 A CN 109632916A CN 201811564438 A CN201811564438 A CN 201811564438A CN 109632916 A CN109632916 A CN 109632916A
- Authority
- CN
- China
- Prior art keywords
- titanium alloy
- material manufacturing
- increasing material
- manufacturing titanium
- sulfuric acid
- 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.)
- Pending
Links
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 53
- 230000001965 increasing effect Effects 0.000 title claims abstract description 46
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 46
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000005259 measurement Methods 0.000 title claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000002161 passivation Methods 0.000 claims abstract description 23
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 claims abstract description 15
- 238000012360 testing method Methods 0.000 claims abstract description 9
- 238000005260 corrosion Methods 0.000 claims description 30
- 230000007797 corrosion Effects 0.000 claims description 30
- 238000001453 impedance spectrum Methods 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 239000003822 epoxy resin Substances 0.000 claims description 7
- 238000001566 impedance spectroscopy Methods 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 229920000647 polyepoxide Polymers 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000011156 evaluation Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000005518 electrochemistry Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/30—Staining; Impregnating ; Fixation; Dehydration; Multistep processes for preparing samples of tissue, cell or nucleic acid material and the like for analysis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/32—Polishing; Etching
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The invention discloses a kind of methods for measuring increasing material manufacturing titanium alloy surface Stability of Passive Film, are specifically implemented according to the following steps: step 1, choosing increasing material manufacturing titanium alloy sample and carry out Passivation Treatment；Step 2, electrochemical impedance spectroscopy test will be carried out through step 1 Passivation Treatment increasing material manufacturing titanium alloy sample；Step 3, the electrochemical impedance spectroscopy result obtained through step 2 is fitted and is parsed.A kind of method of measurement increasing material manufacturing titanium alloy surface Stability of Passive Film of the invention, can effective evaluation increasing material manufacturing titanium alloy passivating film stability in sulfuric acid solution.
Description
Technical field
The invention belongs to technical field of metal material, and it is stable to be related to a kind of measurement increasing material manufacturing titanium alloy surface passivating film
The method of property.
Background technique
Be widely used at present aerospace titanium alloy, with its excellent corrosion resistance, high epistasis title.20th century 50-60
In generation, what main development got up is the high-temperature titanium alloy of aero-engine and the structural titanium alloy of body, is developed the seventies
A collection of corrosion resistant Ti alloy, since the eighties, corrosion resistant Ti alloy and high-strength titanium alloy are further developed, and titanium alloy is mainly used
It is secondly guided missile, the structural member of rocket and high-speed aircraft in production aircraft engine compressor parts.
Titanium is IV B race transition elements, belongs to active metal in electromotive series, at 25 DEG C, for reacting Ti=Ti2++ 2e meter
Calculating resulting standard electrode potential is -1.63V, is thermodynamically extremely unstable metal, but since titanium has high parent to oxygen
And power, it can be formed generate that one layer stable, protectiveness is good, the strong oxidation film of binding force, so that it is very in an oxygen-containing environment
Passive state is presented in more strong corrosive mediums, thus there is excellent corrosion resistance, to be able in practice in industrial production
It is widely applied.
Titanium surface film oxide is often not single structure, but from the TiO of oxidation film surface2Gradually Ti is passed through in transition2O3,
In oxide and metal interface based on TiO, but also there can be the oxide of intermediate non-chemical equivalent, that is to say, that past
Toward the oxidation film for being multilayered structure, it makes the passivation of titanium that following characteristics be presented: (1) critical passive current density is smaller, causes blunt current potential
Relatively negative, be easy passivation has very strong passivation stability again；(2) passive potential region is wide, is not easy to form " transpassivation "；(3) it is passivated state
It is not easy to be destroyed, can be repaired rapidly surface is scratched, so the passivating film of titanium has very high stability.However
Also there is application in some aviation pipeline components, superficial film mistake can occur in long-term pipeline liquid for the titanium oxide layer of titanium alloy
How steady phenomenon, characterize and evaluation is an engineering problem, and the passivating film on surface is impaired and then dissolution unstability occurs, and leads to component
Corrosion failure during military service.
Summary of the invention
The object of the present invention is to provide a kind of methods for measuring increasing material manufacturing titanium alloy surface Stability of Passive Film, can have
Effect evaluation increasing material manufacturing titanium alloy stability in sulfuric acid solution.
The technical scheme adopted by the invention is that a kind of side for measuring increasing material manufacturing titanium alloy surface Stability of Passive Film
Method is specifically implemented according to the following steps:
Step 1, it chooses increasing material manufacturing titanium alloy sample and carries out Passivation Treatment；
Step 2, electrochemical impedance spectroscopy test will be carried out through step 1 Passivation Treatment increasing material manufacturing titanium alloy sample；
Step 3, the electrochemical impedance spectroscopy result obtained through step 2 is fitted and is parsed.
It is of the invention to be further characterized in that,
Step 1 specifically:
Step 1.1, choose increasing material manufacturing titanium alloy sample bar as electrochemical sample, one end as working face, remaining
Part is encapsulated with epoxy resin；
Step 1.2, the electrochemical sample handled through step 1.1 is immersed in containing different concentration Fe3+Sulfuric acid solution
The middle immersion regular hour completes Passivation Treatment；
The electrochemical sample surface chosen in step 1.1 is polishing to 1200# polishing with abrasive paper for metallograph, then with anhydrous second
Alcohol cleans drying after oil removing, then again encapsulates one end with epoxy resin.
Sulfuric acid solution in step 1.2 is that concentration is 44.6% sulfuric acid solution.
Different concentration Fe in step 1.23+Sulfuric acid solution be respectively as follows: Fe3+Concentration be respectively 0.001mol/L,
The sulfuric acid solution of 0.005mol/L, 0.01mol/L, 0.05mol/L, 0.1mol/L, soaking time 30min；
Step 2 specifically:
Step 2.1, under corrosion potential, containing different Fe3+In the sulfuric acid corrosion solution of concentration, with increasing material manufacturing titanium
Alloy sample is as working electrode, and using platinized platinum as auxiliary electrode, saturated calomel electrode is anti-as reference electrode progress electrochemistry
It answers；
Step 2.2, reach stable state in step 2.1 reaction system after 1h to start to carry out electrochemical impedance spectrometry,
Increasing material manufacturing titanium alloy sample is obtained in different Fe3+The impedance spectrum of the sulfuric acid solution of concentration.
Carrying out carrying out electrochemical impedance spectrometry exchange disturbance voltage when being is 10mV, sine wave freuqency range 100kHz
~10mHz.
Step 3 specifically: the impedance spectrum obtained to step 2.2 measurement uses equivalent circuit Rs(Qc(Rc(QdlRct))) or
Person's equivalent circuit Rs(QcRc) be fitted on ZSimpWin software, wherein Rs、Qc、Rc、QdlAnd RctWhat is respectively indicated is sulphur
Acid solution resistance, passivation membrane capacitance, passivation film resistance, double electrolysis layer capacitances and charge transfer resistance.
The beneficial effects of the present invention are: the present invention is existed using the method energy effective evaluation increasing material manufacturing titanium alloy of electrochemistry
Stability in sulfuric acid solution.
Detailed description of the invention
Fig. 1 be in the embodiment of the present invention 1 TC4 in Fe3+AC impedance curve in the sulfuric acid solution of≤0.001mol/L
Figure；
Fig. 2 be in the embodiment of the present invention 1 TC4 in Fe3+AC impedance curve in the sulfuric acid solution of >=0.001mol/L
Figure.
Fig. 3 is equivalent circuit R of the present inventions(Qc(Rc(QdlRct))) circuit diagram；
Fig. 4 is equivalent circuit R of the present inventions(QcRc) circuit diagram.
Fig. 5 equivalent circuit R of the present inventions(QcRc) circuit diagram.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
A method of measurement increasing material manufacturing titanium alloy surface Stability of Passive Film is specifically implemented according to the following steps:
Step 1, it chooses increasing material manufacturing titanium alloy sample and carries out Passivation Treatment；Specifically:
Step 1.1, increasing material manufacturing titanium alloy sample bar is chosen as electrochemical sample, and electrochemical sample surface is used
Abrasive paper for metallograph is polishing to 1200# polishing, dries after then cleaning oil removing with dehydrated alcohol, using one end as working face, remaining part
Divide and is encapsulated with epoxy resin；
Step 1.2, the electrochemical sample handled through step 1.1 is immersed in containing different concentration Fe3+44.6% sulphur
30min is impregnated in acid solution, completes Passivation Treatment；Wherein, different concentration Fe3+Sulfuric acid solution be respectively as follows: Fe3+Concentration point
Not Wei 0.001mol/L, 0.005mol/L, 0.01mol/L, 0.05mol/L, 0.1mol/L sulfuric acid solution；
Step 2, electrochemical impedance spectroscopy test will be carried out through step 1 Passivation Treatment increasing material manufacturing titanium alloy sample；Specifically
Are as follows:
Step 2.1, under corrosion potential, containing different Fe3+In the sulfuric acid corrosion solution of concentration, with increasing material manufacturing titanium
Alloy sample is as working electrode, and using platinized platinum as auxiliary electrode, saturated calomel electrode is anti-as reference electrode progress electrochemistry
It answers；
Step 2.2, reach stable state in step 2.1 reaction system after 1h to start to carry out electrochemical impedance spectrometry,
Exchange disturbance voltage is 10mV, sine wave freuqency range 100kHz~10mHz, obtains increasing material manufacturing titanium alloy sample in difference
Fe3+The impedance spectrum of the sulfuric acid solution of concentration.
Step 3, the electrochemical impedance spectroscopy result obtained through step 2 is fitted and is parsed；Specifically: to step 2.2
The impedance spectrum that measurement obtains uses equivalent circuit Rs(Qc(Rc(QdlRct))) or equivalent circuit Rs(QcRc) soft in ZSimpWin
It is fitted on part, wherein Rs、Qc、Rc、QdlAnd RctWhat is respectively indicated is sulfuric acid solution resistance, passivation membrane capacitance, passivating film
Resistance, double electrolysis layer capacitances and charge transfer resistance.
The principle of the present invention is: being currently widely used for metal electrode measurement system, electrochemical impedance spectroscopy can be accurate, fast
Reflect the passivating film information on the surface TC4 fastly.When passivating film when surface is complete, in etchant solution, impedance spectrum shows as one
A time constant；When passivating film it is imperfect or it is unstable cause to corrode when, impedance spectrum then shows as two time constants,
Wherein the impedance value of low frequency end then can further reactive matrix extent of corrosion.
The electrochemical nature of metallic diaphragm unstability be exactly oxidation on metal surface object electrochemical reaction occurs in the electrolyte and
Caused solution enters matrix phenomenon, and AC impedance method is a kind of transient state electrochemical techniques.In the anode reaction of corrosion system
In, polarization resistance is inversely proportional with corrosion electric current density, is disturbed using sinusoidal ac signal by a small margin, and observe system and exist
Situation is followed to disturbance when stable state, the impedance spectrum of corrosion metal electrode is parsed, available polarization resistance can be with
The size of metal erosion current density is calculated, so as to acquire its corrosion rate.The same metallic surface of the size of interface capacitance
The factors such as state and solution composition are related, and in certain system, the variation of interface capacitance reflects corrosion metal watch planar
The variation of state.So the measurement by AC impedence method to electrode surface interface capacitance, can study corrosion of metal behavior
With the variation of electrode surface state.Ac impedance technology is substantially the feature studied RC circuit in the case where exchanging electro ultrafiltration and answers
With.This method measures corrosion rate and inquires into corrosion inhibiter to metal erosion for the anodic dissolution processes of research metal
The influence of journey has unique superiority.This method is a kind of Detection of Weak Signals, and the influence to metal surface state is little, and
Its test frequency range can be very wide, is relatively suitble to measurement low speed corrosion system, but be susceptible to corrosion system stability
It influences.
Embodiment 1
TC4 is measured in various concentration Fe3+44.6% sulfuric acid solution middle impedance spectral curve.
Step 1, processing is passivated to increasing material manufacturing titanium alloy TC 4.
Step 1.1, it chooses increasing material manufacturing titanium alloy TC 4 (Ti6Al4V) specific ingredient and is shown in Table 1, electrochemical sample specification is
10mm × 10mm × 3mm, one end are working face, and rest part is encapsulated with epoxy resin, and specimen surface is polishing to abrasive paper for metallograph
1200#, polishing, and oil removing is cleaned with dehydrated alcohol, it is dry；
1 TC4 chemical component of table
Step 1.2, sample is immersed in containing different concentration Fe3+Sulfuric acid solution in, Fe3+Concentration is respectively
0.001mol/L, 0.005mol/L, 0.01mol/L, 0.05mol/L, 0.1mol/L, soaking time 30min；
Step 2, increasing material manufacturing titanium alloy TC 4 electrochemical impedance spectroscopy is tested；
Step 2.1, electrochemical impedance test carries out under corrosion potential, is containing different Fe3+The sulfuric acid corrosion of concentration is molten
In liquid, working electrode is increasing material manufacturing titanium alloy TC 4, and auxiliary electrode is platinized platinum, and reference electrode is saturated calomel electrode (SCE)；
Step 2.2, system reaches stable state progress electrochemical impedance spectrometry after 1h.Exchanging disturbance voltage is
10mV, sine wave freuqency range 100kHz~10mHz, impedance spectrum test result are as depicted in figs. 1 and 2.
It is as follows to impedance spectrum test result analysis, as shown in Figure 1, in 44.6% sulfuric acid and Fe3+Content it is less (≤
0.001mol/L), EIS spectrum shows two time constants, and what the circular arc of medium-high frequency represented is the information of passivating film, and low
What the circular arc of frequency part represented is the information of matrix, since having there is matrix information time constant, then corrosive medium has been at this time
Passivating film/metal interface is reached, matrix corrosion has occurred and that can measuring passivating film, stability is very poor in the case；Work as Fe3+
When content higher (>=0.005mol/L), impedance spectrum is made of the capacitive reactance arc of a time constant, shows TC4 in this solution
Middle passivating film is very stable, and corrosive medium cannot pass through passivating film and reach metal interface.
Step 3, electrochemical impedance spectroscopy is fitted and parses, with using equivalent circuit Rs(Qc(Rc(QdlRct))) or
Equivalent circuit Rs(QcRc), as shown in Figure 3 and Figure 4, impedance modal data is fitted using ZSimpWin software, wherein Rs、
Qc、Rc、QdlAnd RctWhat is respectively indicated is that solution resistance, passivation membrane capacitance, passivation film resistance, double electrolysis layer capacitances and charge turn
Resistance is moved, each parameter of gained is as shown in table 2；
2 TC4 of table is containing various concentration Fe3+44.6wt% sulfuric acid electrical equivalent fit parameter values
It can find out from 2 Equivalent Circuit Fitting value of table, with Fe in the sulfuric acid solution of concentration3+The increase of concentration, passivation film electricity
Resistance Rc is significantly increased.In 44.6% sulfuric acid solution, RCFor 109.5 Ω .cm-2；And work as Fe3+Concentration is 0.005mol/L, RC
It is 4.282 × 104Ω.cm-2, film layer resistance increases, and the decline of film layer corrosion current, membranous layer stability is obviously improved, this and impedance
It is consistent that spectral curve time constant evaluates film layer stability result.
Embodiment 2
In view of Fe3+It can become Fe after oxidation2+, it is comparative analysis, sample is placed in the Fe of various concentration2+Sulfuric acid it is molten
Electrochemistry experiment is carried out in liquid, due to Fe2+It is oxidizable, nitrogen charging processing is carried out to it, measures TC4 in various concentration Fe2+Resistance
Anti- spectral curve measures TC4 in various concentration Fe3+44.6% sulfuric acid middle impedance spectral curve.
Step 1, processing is passivated to increasing material manufacturing titanium alloy TC 4.
Step 1.1, it chooses increasing material manufacturing titanium alloy TC 4 (Ti6Al4V) specific ingredient and is shown in Table 1, the specification of electrochemical sample
For 10mm × 10mm × 3mm, one end is working face, and rest part is encapsulated with epoxy resin, and specimen surface is polished with abrasive paper for metallograph
It to 1200#, polishes, and cleans oil removing with dehydrated alcohol, it is dry；
Step 1.2, sample is immersed in containing different concentration Fe2+Sulfuric acid solution in, Fe2+Concentration is respectively
0.001mol/L, 0.005mol/L, 0.01mol/L, 0.05mol/L, 0.1mol/L, soaking time 30min；
Step 2, increasing material manufacturing titanium alloy TC 4 electrochemical impedance spectroscopy is tested, and impedance curve is shown in Fig. 3.
Step 2.1, electrochemical impedance test carries out under corrosion potential, is containing different Fe2++The sulfuric acid corrosion of concentration
In solution, working electrode is increasing material manufacturing titanium alloy TC 4, and auxiliary electrode is platinized platinum, and reference electrode is saturated calomel electrode
(SCE), it while carrying out carrying out nitrogen charging processing to it.
Step 2.2, system reaches stable state progress electrochemical impedance spectrometry after 1h；Exchanging disturbance voltage is
10mV, sine wave freuqency range 100kHz~10mHz；TC4 is in Fe containing various concentration2+Sulfuric acid solution in impedance spectrum, such as Fig. 3
It is shown, with it in 44.6% sulfuric acid and Fe3+Content is less (≤0.001mol/L), as shown in Figure 1, similar, EIS spectrum shows
Two time constants, what the circular arc of medium-high frequency represented is the information of passivating film, and what the circular arc of low frequency part represented is matrix
Information, corrosive medium has arrived at passivating film/metal interface at this time, and matrix corrosion has occurred and that.
Step 3, electrochemical impedance spectroscopy is fitted and parses, with equivalent circuit Rs(Qc(Rc(QdlRct))) (Fig. 4) progress
It is fitted, wherein Rs、Qc、Rc、QdlAnd RctWhat is respectively indicated is solution resistance, appearance passivating film electricity, passivation film resistance, double electrolyte layers
Capacitor and charge transfer resistance it is as shown in table 3 to be fitted each parameter of gained with ZSimpWin software, known to contrast table 2,3
In 44.6% sulfuric acid solution, RCFor 109.5 Ω cm-2；And work as Fe3+Concentration is 0.005mol/L, RCIt is 4.282 × 104
Ω·cm-2, film layer resistance significantly increases, and stability enhancing, corrosion resistance improve.
3 TC4 of table is containing various concentration Fe2+44.6wt% sulfuric acid electrical equivalent fit parameter values
| Medium | Rs/(Ω.cm-2) | Qc/(Ω.cm-2) | Rc/(Ω.cm-2) | Qdl/(μF.cm-2) | Rct/(Ω.cm-2) |
| 44.6% sulfuric acid | 2.95 | 2.05×10-4 | 109.5 | 1.038×10-3 | 59.89 |
| 44.6 sulfuric acid+0.001mol/ LFe2+ | 1.61 | 1.63×10-4 | 395.1 | 0.8863 | 249.5 |
| 44.6 sulfuric acid+0.005mol/ LFe2+ | 2.39 | 2.03×10-4 | 315.2 | 0.7228 | 159.7 |
| 44.6 sulfuric acid+0.01mol/ LFe2+ | 1.42 | 2.62×10-4 | 20.71 | 0.05351 | 134.3 |
Claims (9)
1. a kind of method for measuring increasing material manufacturing titanium alloy surface Stability of Passive Film, which is characterized in that specifically according to following step
It is rapid to implement:
Step 1, it chooses increasing material manufacturing titanium alloy sample and carries out Passivation Treatment；
Step 2, electrochemical impedance spectroscopy test will be carried out through step 1 Passivation Treatment increasing material manufacturing titanium alloy sample；
Step 3, the electrochemical impedance spectroscopy result obtained through step 2 is fitted and is parsed.
2. a kind of method for measuring increasing material manufacturing titanium alloy surface Stability of Passive Film according to claim 1, feature
It is, the step 1 specifically:
Step 1.1, increasing material manufacturing titanium alloy sample bar is chosen as electrochemical sample, and one end is as working face, rest part
It is encapsulated with epoxy resin；
Step 1.2, the electrochemical sample handled through step 1.1 is immersed in containing different concentration Fe3+Sulfuric acid solution in soak
The regular hour is steeped, Passivation Treatment is completed.
3. a kind of method for measuring increasing material manufacturing titanium alloy surface Stability of Passive Film according to claim 2, feature
It is, the electrochemical sample surface chosen in the step 1.1 is polishing to 1200# with abrasive paper for metallograph and polishes, then with anhydrous second
Alcohol cleans drying after oil removing, then again encapsulates one end with epoxy resin.
4. a kind of method for measuring increasing material manufacturing titanium alloy surface Stability of Passive Film according to claim 2, feature
It is, the sulfuric acid solution in the step 1.2 is that concentration is 44.6% sulfuric acid solution.
5. a kind of method for measuring increasing material manufacturing titanium alloy surface Stability of Passive Film according to claim 2, feature
It is, the different concentration Fe in the step 1.23+Sulfuric acid solution be respectively as follows: Fe3+Concentration be respectively 0.001mol/L,
The sulfuric acid solution of 0.005mol/L, 0.01mol/L, 0.05mol/L, 0.1mol/L, soaking time 30min.
6. a kind of method for measuring increasing material manufacturing titanium alloy surface Stability of Passive Film according to claim 5, feature
It is, the step 2 specifically:
Step 2.1, under corrosion potential, containing different Fe3+In the sulfuric acid corrosion solution of concentration, with the examination of increasing material manufacturing titanium alloy
Sample is as working electrode, and using platinized platinum as auxiliary electrode, saturated calomel electrode is electrochemically reacted as reference electrode；
Step 2.2, reach stable state in step 2.1 reaction system after 1h to start to carry out electrochemical impedance spectrometry, obtain
Increasing material manufacturing titanium alloy sample is in different Fe3+The impedance spectrum of the sulfuric acid solution of concentration.
7. a kind of method for measuring increasing material manufacturing titanium alloy surface Stability of Passive Film according to claim 6, feature
It is, carries out the progress electrochemical impedance spectrometry to exchange disturbance voltage when being being 10mV, sine wave freuqency range 100kHz
~10mHz.
8. a kind of method for measuring increasing material manufacturing titanium alloy surface Stability of Passive Film according to claim 6, feature
It is, the step 3 specifically: the impedance spectrum obtained to step 2.2 measurement uses equivalent circuit Rs(Qc(Rc(QdlRct))) or
Person's equivalent circuit Rs(QcRc) be fitted on ZSimpWin software, wherein Rs、Qc、Rc、QdlAnd RctWhat is respectively indicated is sulphur
Acid solution resistance, passivation membrane capacitance, passivation film resistance, double electrolysis layer capacitances and charge transfer resistance.
9. a kind of method for measuring increasing material manufacturing titanium alloy surface Stability of Passive Film according to claim 9, feature
It is, in Fe3+≤ 0.001mol/L uses equivalent circuit Rs(Qc(Rc(QdlRct))), Fe3+>=0.005mol/L uses equivalent electricity
Road Rs(QcRc)。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811564438.7A CN109632916A (en) | 2018-12-20 | 2018-12-20 | A method of measurement increasing material manufacturing titanium alloy surface Stability of Passive Film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811564438.7A CN109632916A (en) | 2018-12-20 | 2018-12-20 | A method of measurement increasing material manufacturing titanium alloy surface Stability of Passive Film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109632916A true CN109632916A (en) | 2019-04-16 |
Family
ID=66075964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811564438.7A Pending CN109632916A (en) | 2018-12-20 | 2018-12-20 | A method of measurement increasing material manufacturing titanium alloy surface Stability of Passive Film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109632916A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110618088A (en) * | 2019-08-12 | 2019-12-27 | 中车青岛四方机车车辆股份有限公司 | Metal material surface passive film testing device |
| CN113340945A (en) * | 2021-04-30 | 2021-09-03 | 武汉工程大学 | Electrochemical detection method for structure and performance of extraction membrane and pervaporation membrane |
| CN114136878A (en) * | 2021-10-25 | 2022-03-04 | 上海氢晨新能源科技有限公司 | Method for testing corrosion resistance of fuel cell metal bipolar plate coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103364243A (en) * | 2013-07-12 | 2013-10-23 | 中国科学院金属研究所 | Preparation method of titanium alloy surface passivation film transmission observation sample |
| CN103543097A (en) * | 2013-11-05 | 2014-01-29 | 广东电网公司电力科学研究院 | Electrochemical method for determining inter-crystalline corrosion sensibility of austenitic stainless steel |
-
2018
- 2018-12-20 CN CN201811564438.7A patent/CN109632916A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103364243A (en) * | 2013-07-12 | 2013-10-23 | 中国科学院金属研究所 | Preparation method of titanium alloy surface passivation film transmission observation sample |
| CN103543097A (en) * | 2013-11-05 | 2014-01-29 | 广东电网公司电力科学研究院 | Electrochemical method for determining inter-crystalline corrosion sensibility of austenitic stainless steel |
Non-Patent Citations (1)
| Title |
|---|
| 王雷 等: "硫酸溶液中Fe3+对TC4腐蚀行为的影响", 《腐蚀与防护》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110618088A (en) * | 2019-08-12 | 2019-12-27 | 中车青岛四方机车车辆股份有限公司 | Metal material surface passive film testing device |
| CN110618088B (en) * | 2019-08-12 | 2021-11-12 | 中车青岛四方机车车辆股份有限公司 | Metal material surface passive film testing device |
| CN113340945A (en) * | 2021-04-30 | 2021-09-03 | 武汉工程大学 | Electrochemical detection method for structure and performance of extraction membrane and pervaporation membrane |
| CN114136878A (en) * | 2021-10-25 | 2022-03-04 | 上海氢晨新能源科技有限公司 | Method for testing corrosion resistance of fuel cell metal bipolar plate coating |
| CN114136878B (en) * | 2021-10-25 | 2024-01-09 | 上海氢晨新能源科技有限公司 | Method for testing corrosion resistance of fuel cell metal bipolar plate coating |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109632916A (en) | A method of measurement increasing material manufacturing titanium alloy surface Stability of Passive Film | |
| CN1952645B (en) | Binode polarization curve method for measuring electrochemical characteristic and corrosion resistance of metal | |
| Badawy et al. | Effect of Ni content on the corrosion behavior of Cu–Ni alloys in neutral chloride solutions | |
| Keddam et al. | Electrochemical Behavior of Passive Iron in Acid Medium: I. Impedance Approach | |
| CN101552141A (en) | Method for manufacturing solid electrolytic capacitor | |
| CN104611751A (en) | Micro-arc oxidation self-assembly composite membrane layer on surface of magnesium alloy and preparation method of micro-arc oxidation self-assembly composite membrane layer | |
| EP2469641B1 (en) | Dye-sensitized solar cell and method for manufacturing the same | |
| Hepel et al. | Chronoamperometric transients at the stationary disk microelectrode | |
| CN105185601A (en) | Titanium dioxide nanotube/polyaniline composite electrode, preparation and application thereof | |
| CN113106515B (en) | Preparation method of corrosion-resistant coating on surface of metal material, product and application thereof | |
| CN104264196A (en) | Method for preparing super-hydrophobic membrane layer on surface of magnesium alloy through one-step method as well as alloy and application of uper-hydrophobic membrane layer | |
| CN110644026B (en) | Preparation method of super-hydrophobic aluminum alloy surface with self-repairing characteristic | |
| Li et al. | Enhancing pitting corrosion resistance of severely cold-worked high nitrogen austenitic stainless steel by nitric acid passivation | |
| CN108344679A (en) | A method of characterization cast austenitic-ferritic stainless steel pitting corrosion | |
| Contractor et al. | Estimation of equilibrium capacitance of polyaniline films using step voltammetry | |
| Yang et al. | Passivity study of titanium alloy TA2 in simulated seawater solution | |
| Pan et al. | Characteristics of electric double layer in different aqueous electrolyte solutions for supercapacitors | |
| Liao et al. | Magnetic field effects on electrochemical dissolution behavior and surface quality of electrochemical machining of Ti-48Al-2Cr-2Nb alloy | |
| CN109559901A (en) | Polypyrrole/molybdenum/titania nanotube ternary composite electrode preparation method | |
| Stevic et al. | Comparative analysis of dynamic electrochemical test methods of supercapacitors | |
| CN110629266A (en) | Preparation method of super-hydrophobic stainless steel surface with self-repairing characteristic | |
| Ferreira et al. | Influence of ethanol, acidity and chloride concentration on the corrosion resistance of AISI 316L stainless steel | |
| Mogoda et al. | Formation and dissolution behaviour of ZrO2 film in H3PO4 acid solutions | |
| CN107964676A (en) | A kind of preparation method of aluminium oxide super hydrophobic surface | |
| El-Egamy | Electrochemical behavior of antimony and antimony oxide films in acid solutions |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190416 |
|
| RJ01 | Rejection of invention patent application after publication |