CN1026017C - Corrosion inhibitor for ironware cultural relic - Google Patents
Corrosion inhibitor for ironware cultural relic Download PDFInfo
- Publication number
- CN1026017C CN1026017C CN 92108521 CN92108521A CN1026017C CN 1026017 C CN1026017 C CN 1026017C CN 92108521 CN92108521 CN 92108521 CN 92108521 A CN92108521 A CN 92108521A CN 1026017 C CN1026017 C CN 1026017C
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- CN
- China
- Prior art keywords
- bta
- ironware
- cultural relic
- inhibiter
- corrosion inhibitor
- 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.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
In the field of ironware cultural relic protection, people take much account of certain organic corrosion inhibitors such as amines, a tannic acid, etc. The present invention goes off the beaten track, and obtains unexpected effects by utilizing benzotriazole (BTA) as the corrosion inhibitor for the ironware cultural relic protection. Experiments prove that the BTA has higher corrosion inhibition efficiency under the condition of lower concentration and has no defect of color change of the ironware caused by the tannic acid. Furthermore, the BTA has the advantages of low toxicity, low cost, etc., and is an ideal corrosion inhibitor for the ironware cultural relic protection.
Description
The invention belongs to chemical technology field, is a kind of corrosion inhibitor for ironware cultural relic.
Ironware is as the bronze work sign in a period after period, use to reach thousands of years so far, its feature be to use extensively and the historical relic number of packages many, its importance in cultural heritage is conspicuous.
Take a broad view of the method for general ironware protection, plating, paint, oiling, inhibiter or the like are arranged.In view of historical relic's protection requires not change original appearance, seemingly having inhibition (agent) method only is present propagable method.
In order to protect ironware cultural relic, can consider various suitable inhibiter in principle.Through screening, what people considered morely is some organic inhibitors, as amine and Weibull etc.It is best amine inhibitor that nineteen eighty-two R.Walker recommends cyclohexylamine carbonate and nitrite cyclohexylamine.When practical application, cyclohexylamine carbonate and dicyclohexyl amine nitrite are to use with the form of mixture.But this synergistic corrosion inhibitor does not appear in the newspapers in the literature to the inhibition efficiency of ironware (or steel) under various concentration.In addition, the toxicity of dicyclohexyl amine nitrite is too big.These all are the where the shoe pinches that this kind inhibiter is applied.In addition, people have proposed to use the corrosion inhibitor for ironware cultural relic based on Weibull, and the difficulty that this prescription is given prominence in implementing is the color that the complexing product of intense violet color has seriously changed ironware.Be not difficult to find out from above report, further study existing inhibiter and seek the urgent task that new inhibiter is the protection ironware cultural relic.
The present invention is devoted to the improvement of the problems referred to above.Because BTA is a kind of slightly acidic material, and in traditional concept, thinks that BTA is the same with general weak acid, may play corrosive nature to ironware.Therefore, do not expect the inhibiter as ironware cultural relic with BTA.The present invention can be used for corrosion inhibitor for ironware cultural relic through a large amount of experiments and practical application several times with reliable digital proof BTA.
BTA inhibiter used water or acetone or ethanol is as the solvent obtain solution, and the weight ratio of BTA and solvent the experiment proved that between 1: 100 to 30: 100, when proportioning at 1: 100 between 10: 100 the time, its corrosion-retarding technique effect is better.
The present invention has selected nearly ten kinds of ironware inhibiter and BTA has carried out a large amount of contrast experiments on A-3 soft steel sample, and experimental result is as follows:
One, temperature programmed desorption experiment:
Measuring result is listed in table 1(experimental technique and is seen " catalysis journal " 2[4 such as Li Quan sesame] (1981) 289) (table 1 is seen the literary composition back)
The data declaration of table 1, the desorption peaks maximum peak temperature of benzotriazole (BTA) is more than 300 ℃, and therefore, experimental data meets following reasoning: good inhibiter should have the maximum peak temperature of higher main desorption peaks.
Two, saline fog method experiment: (experimental technique is seen Guo Lan etc., whole nation archaeology and cultural relic protecting chemical seminar collection of thesis summary Xi'an in 1989,29 pages) measuring result is listed in table 2(table 2 and is seen the literary composition back)
Mixed inhibitor in the table is cyclohexylamine carbonate and dicyclohexyl amine nitrite
Three, weighting method experiment:
1, lists in table 3(table 3 with the squeegee process measuring result and see the literary composition back)
2, list in table 4, table 5(weighting method according to U.S. ASTMG31-72 canonical measure with the infusion method measuring result) (table 4,5 is seen the literary composition back)
Four, method of polarization curve experiment:
Measuring result is listed in table 6, table 7(table 6,7 is seen the literary composition back)
Take a broad view of the data of surveying with saline fog method, weighting method and method of polarization curve, BTA is undoubtedly inhibiter preferably; Weibull also has the possibility of use, but the colour-change on surface is big, and this is the where the shoe pinches that is used for historical relic's protection.
Therefore, lot of experiment results shows that benzotriazole (BTA) is compared with other inhibiter has tangible advantage, simultaneously because BTA has the inhibition efficiency height, toxicity is low, advantages such as easy acquisition, and other inhibiter is a more efficiently soft steel inhibiter relatively.Through practical application on ironware cultural relic, obtained fabulous effect, be a kind of practicality and comparatively ideal corrosion inhibitor for ironware cultural relic.
Embodiment:
1, certain Military Museum is used for the test of weapon and instrument, and BTA is 1: 50 with the ratio of organic solvent.
2, certain Provincial Museum is to the test of pistol, and BTA is 1: 10 with the ratio of organic solvent.
3, certain museum, county is used for the sabre of 50 cm long, and the band rust is handled, and BTA is 1: 30 with the ratio of organic solvent.
More than three lists confirm that all the color and the feel of historical relic do not have considerable change after BTA handles, and meet historical relic's protection requirement etc.Also claim that " treated sample can all be removed and do not make example weight that considerable change (reduction be about ten thousand/) is arranged with ethanol, and reversibility is fine coating in the operation report in museum.”
Because the etching condition that uses among the present invention has the effect of accelerated corrosion, estimate that BTA has preferably long-term corrosion mitigating effect to mild steel class ironware cultural relic under collection condition. The instrument collection of certain Military Museum behind brushing BTA, through one month store, has found out than brushing person not to have obvious rust-proofing ability.
Table 1 temperature programmed desorption result of the test
Numbering adsorbate chromatography room temperature (℃) main desorption peaks maximum peak temperature (℃)
1 cyclohexylamine 140 326
2 cyclohexanone 150 284,547
3 ethyl acetoacetates 170 364
4 imidazoles 190 316
5 carbazoles 300＜50
6 BTAs 200 316
7 cyclohexylamine carbonates 300 216
8 dicyclohexyl amine nitrites 300 242
9 tannic acid 300 556
The time that occurs rust class in table 2 salt mist experiment at sample
Corrosion inhibiter cyclohexanone ethyl acetoacetate imidazoles carbazole BTA
T(hour) 10 18 37 10 118
Inhibiter trimeric cyanamide mixed inhibitor Weibull blank
T(hour) 166 28 96 22
The weightless # of the weightless data * of sample * under some inhibiter effects of table 3
Time (h) 48 96 114 192 264 336
Reagent
Hexahydroaniline 0.2188 0.3470 0.5103 0.6687 0.9821 1.283
Pimelinketone 0.2866 0.4316 0.5824 0.7526 1.076 1.421
Methyl aceto acetate 0.2541 0.4506 0.6088 0.7566 1.059 1.377
Imidazoles 0.2595 0.2892 0.5169 0.6527 1.009 1.315
Carbazole 0.2379 0.3902 0.5284 0.6718 1.030 1.413
Benzotriazole 0.1618 0.1990 0.2663 0.4022 0.5974 0.8431
Trimeric cyanamide 0.1684 0.3366 0.5649 0.7530 0.9349 1.282
Mixed inhibitor * 0.2254 0.3568 0.5108 0.7064 0.9489 1.297
Weibull 0.1320 0.2403 0.3045 0.3756 0.6152 0.8170
Check sample 0.2690 0.4460 0.5891 0.7528 1.016 1.424
* mixed inhibiter is cyclohexylamine carbonate and dicyclohexyl amine nitrite.
The * corrosion is what to carry out under 21-27 ℃ room temperature.
# represents mg/cm
2
Table 4 sample is 1 * 10
-2Weightless data * in the M BTA solution (temperature 10-25 ℃)
Sample sample 2 samples 3
Blank 1 blank 2 blank 3 samples 1
Time (d) (1 * 10
-2M)
2 0.2094 0.1733 0.1739 0.0503 0.0339 0.0517
5 0.3490 0.2946 0.3652 0.0670 0.0508 0.0517
8 0.5236 0.5373 0.5217 0.0838 0.0678 0.0690
13 0.7853 0.8319 0.7652 0.1005 0.0847 0.0862
19 1.100 1.196 1.200 0.1507 0.1186 0.1034
26 1.798 1.889 1.881 0.3517 0.3220 0.2931
34 2.600 2.652 2.661 0.5695 0.5085 0.5000
43 3.525 3.484 3.600 1.055 1.017 1.000
# represents mg/cm
2
Table 5, sample be at 0.1M BTA and 5%NaHCO, temperature 18-22 ℃ of the weight loss among the 0.1M BTA (milligram)
Time (my god) blank 1 blank 2 blank 345
（6.882） （6.664） （6，.763） （6.787） （6.713）
4 3.7 4.3 4.3 -4.5 -4.0
7 6.2 6.5 6.5 -6.0 -4.0
14 10.6 10.6 12.4 -7.5 -5.1
Time (my god) 6789
（6.650） （6.620） （6.730） （6.724）
4 -1.6 -1.6 -2.8 -1.9
7 -2.4 -1.6 -2.3 -1.2
14 -5.7 -3.6 -3.6 -3.7
1, the corrosive fluid of 2, No. 3 (blank) samples is 3.5% sodium-chlor.
4, the corrosive fluid of 5, No. 6 samples is that 0.1M BTA(medium is 3.5% sodium-chlor).
7, the corrosive fluid of 8, No. 9 samples is 5% sodium bicarbonate/0.1M BTA/3.5% sodium-chlor.
Be the long-pending (cm of specimen surface in () bracket
2).
The inhibition efficiency P(% of several inhibiter that table 6 polarization varicose method is surveyed)
Concentration (M) 1.0 * 10
-51.0 * 10
-41.0 * 10
-31.0 * 10
-21.0 * 10
-1
Hexahydroaniline 11.1 44.4 96.8～100～100
Pimelinketone 68.3 82.5 20.6 // * *
Methyl aceto acetate 73.0 71.4 31.7 71.4/* *
Imidazoles 93.7 82.5 93.7 96.8 95.2
Carbazole 36.7 43.0/29.0/
Benzo three cyanamides 79.7 93.7 92.9 99.0 92.0
Trimeric cyanamide 20.3 55.7 74.7 92.0/
Mixed inhibitor # 20.3 20.3 87.3 99.5/
Weibull 29.1 36.7 10.1 //
* pimelinketone and methyl aceto acetate are 1 * 10
-1During M, P is a negative value in the actual measurement.
The # mixed inhibitor is cyclohexylamine carbonate and dicyclohexyl amine nitrite.
The inhibition efficiency of the BTA that table 7, polarization curve and weighting method are measured
Concentration (M) 1.0 * 10
-51.0 * 10
-41.0 * 10
-31.0 * 10
-2
LogI. -4.12 -4.20 -4.33 -5.30
Io（A/cm） 7.6×10
-56.3×10
-54.7×10
-55.0×10
-5
P（%） 0 16.9 38.3 85.5
P＃（%） / 4.0 41.2 90
The inhibition efficiency of P# for being surveyed with weighting method (infusion method).
Claims (3)
1, a kind of ironware inhibiter is characterized in that this inhibiter is to form in 1: 100～30: 100 by benzotriazole with as the water of solvent, acetone or alcohol with weight ratio.
2, inhibiter according to claim 1, the weight ratio that it is characterized in that benzotriazole and solvent is 1: 100～10: 100.
3, be coated on according to claim 1,2 described inhibiter and carry out anti-corrosion protection on the ironware surface.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108521 CN1026017C (en) | 1992-07-28 | 1992-07-28 | Corrosion inhibitor for ironware cultural relic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92108521 CN1026017C (en) | 1992-07-28 | 1992-07-28 | Corrosion inhibitor for ironware cultural relic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1070956A CN1070956A (en) | 1993-04-14 |
| CN1026017C true CN1026017C (en) | 1994-09-28 |
Family
ID=4943618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92108521 Expired - Fee Related CN1026017C (en) | 1992-07-28 | 1992-07-28 | Corrosion inhibitor for ironware cultural relic |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1026017C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1081248C (en) * | 1998-06-12 | 2002-03-20 | 中国科学院武汉岩土力学研究所 | Process for removing harmful rust from bronze articles with ammonia water and cyanide |
| CN107136075B (en) * | 2017-05-08 | 2020-06-09 | 任春山 | Dual-protection antibacterial and anticorrosive aerosol for ancient metal cultural relics and application thereof |
-
1992
- 1992-07-28 CN CN 92108521 patent/CN1026017C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1070956A (en) | 1993-04-14 |
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