CN104568721B - Acceleration test and equivalence estimation method of simulation coating under marine atmospheric environment - Google Patents

Acceleration test and equivalence estimation method of simulation coating under marine atmospheric environment Download PDF

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CN104568721B
CN104568721B CN201510032599.1A CN201510032599A CN104568721B CN 104568721 B CN104568721 B CN 104568721B CN 201510032599 A CN201510032599 A CN 201510032599A CN 104568721 B CN104568721 B CN 104568721B
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test
coating system
aberration
condition
coating
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CN104568721A (en
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向江涛
罗来正
杨小奎
肖勇
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No 59 Research Institute of China Ordnance Industry
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Abstract

The invention discloses an acceleration test and equivalence estimation method of a simulation coating under marine atmospheric environment. The method comprises the following steps: sequentially performing multi-factor synergy test and salt spray test, and performing combined circulation. One test circulation cycle is 6 days, wherein one cycle of the multi-factor synergy test is 5 days and one cycle of the salt spray test is 1 day. The method is characterized in that conversion coefficients of the coating color difference or the light loss rate between the combined acceleration test in a laboratory and the marine atmospheric environment test are established, when the coating ageing mechanisms are essentially consistent under acceleration test and marine atmospheric environment, the color difference or the light loss rate during the marine atmospheric test is equivalently estimated by the acceleration test data in the laboratory under the same coating and the solar radiation, and the acceleration ratio can reach more than 8 times; the estimation result of the coating performance change is compared with the atmospheric exposure test result, and the error is less than 15%.

Description

Accelerated test and equivalent appraisal procedure of a kind of simulation coating in naval air environment
Technical field
The present invention relates to a kind of simulation coating is particularly related in the accelerated test and equivalent appraisal procedure of naval air environment And a kind of multiple-factor circulation combination accelerated test method for coating naval air environment adaptability Fast Evaluation and equivalent comment Estimate the change of coating performance under naval air environment.
Background technology
Coating is one of most economical effective means of the anticorrosions such as metal material, industrial products, the quality of its resistance to ag(e)ing Directly affect stablizing for properties of product.Mass data shows that coating is in use due to being subjected to the comprehensive of various environmental factorss Group photo rings and catabiosis occurs, and especially high radiation, high temperature, high humidity, the naval air environment of high salt fog are more easy to send out coating Raw performance degradation, produces the catabiosis such as loss of gloss, discoloration, efflorescence and foaming, has a strong impact on properties of product and attractive in appearance, for market The consideration of competition, each manufacturer add in the urgent need to obtaining the multiple-factor that can be used for Fast simulation naval air environment exposure test combination Fast test method, and can be quick to reach in the method for equivalent assessment coating main performance change in naval air environment Screening, improvement and the purpose for optimizing coating.
At present, the accelerated test of laboratory simulation naval air environment is most of only considers single environment factor or multiple lists One environmental condition factor is sequentially applied to coating surface, it is impossible to which, very well under simulated marine atmosphere environment, each environmental factorss are simultaneously comprehensive Conjunction is applied to the situation of coating surface, the particularly multiple-factor such as solar radiation, alternation of wetting and drying, temperature cycles synergism to applying The impact of layer, has had a strong impact on the practicality of the reliability and test method of result of the test.
The content of the invention
Present invention aim at accelerated test and equivalent appraisal procedure of a kind of simulation coating in naval air environment are provided, The laboratory simulation accelerated test method that simulation is good, test period is short can be provided, and can be accelerated in this laboratory simulation On the basis of the test data that test is provided, equivalent assessment coating specifies aberration or mistake under solar radiation quantity in naval air environment The change of light rate.
The first object of the present invention is achieved through the following technical solutions:
A kind of accelerated test method of simulation coating in naval air environment, it is characterised in that:Multiple-factor association is carried out successively With test, salt spray test, and it is combined circulation.
The time of test cycle is 6 days, wherein, the multiple-factor Synergism Testing a cycle test period is 5 days, Salt spray test a cycle test period is 1 day.
The experimental condition of the salt spray test is:35 DEG C of vapo(u)rizing temperature, 5% NaCl solution, dilute hydrochloric acid are adjusted to pH= 4.5~5.5;
The multiple-factor Synergism Testing a cycle test includes 5 circulations, and circulation every time is followed using solar radiation, temperature Alternately three kinds of factors act synergistically on coating for ring and moistening-drying, then make coating keep condensation in no light condition.
Described each cycle period of multiple-factor Synergism Testing is 24h, wherein:
The solar radiation condition:0h is to 20h illumination, light source:1120 ± 10%W/m2, 20h- 24h closings Light source;
The Thermal cycling conditions:0h is to 8h high temperature:44 DEG C of illumination, 8h to 20h coolings:Under illumination condition, 44 DEG C drop to 34 DEG C, and 20h to 21h keeps 1h low temperature:34 DEG C are unglazed, and 21h to 24h carries out 3h intensifications, under no light condition, 34 DEG C are raised to 44 DEG C, and any of the above-described stage relative humidity is all higher than equal to 90%;
The moistening-be dried alternation condition:Carry out moistening under illumination condition-alternating action is dried, using air condensation Moistened, drying is realized in illumination, be the alternate cycles for moistening-being dried per 4h, moistening is 1 with the time scale being dried: 3, moisten for totally 5 times under 20h illumination conditions-it is dried alternate cycles;
No light condition keeps condensation condition:In the no light time 4h of 20h to 24h, condensation is carried out using air.
In order to realize above-mentioned second purpose, employ the following technical solutions:
Accelerated test equivalent appraisal procedure of a kind of simulation coating in naval air environment, initially with above-mentioned test side Method is tested, it is characterised in that:
After circulation composite test terminates every time, detection obtains coating performance delta data;
Determine reference coating;
The reference coating aberration set up under laboratory combination identical with the naval air environment solar radiation quantity of accelerated test or The conversion coefficient of gloss loss;
Using accelerated test aberration or gloss loss and the equivalent assessment of the product of reference coating aberration or gloss loss conversion coefficient Coating aberration or gloss loss change under naval air environment.
The conversion coefficient of the reference coating aberration or gloss loss is the ginseng when two kinds of experimental enviroment solar radiation quantities are identical Than coating ratio in both environments between corresponding aberration or gloss loss, computational methods answer coincidence formula (1):
K=A/B (1)
In formula:
K --- reference coating aberration or gloss loss conversion coefficient;
A --- the corresponding reference coating aberration of experimental enviroment A or gloss loss value;
B --- the corresponding reference coating aberration of experimental enviroment B or gloss loss value.
The employing accelerated test aberration or gloss loss are equivalent with the product of reference coating aberration or gloss loss conversion coefficient Coincidence formula (2) is answered in coating aberration or gloss loss change under assessment naval air environment:
Y=K × X (2)
In formula:
The aberration or gloss loss Pre-Evaluation value of Y --- coating marine atmosphere exposure test;
K --- reference coating aberration or gloss loss conversion coefficient;
X --- specify under solar radiation quantity, combine the measured value of aberration or gloss loss in accelerated test.
As a result of above-mentioned technical proposal, the present invention has the advantage that:
The present invention is by analyzing the environmental key-element intensity played a crucial role to coating aging in naval air environment, frequency occurring Rate and time scale, by solar radiation, temperature cycles and moistening-drying, alternately multi-environment factor acts on coating simultaneously, truly Reproduce what coating daytime under naval air environment, caused light degradation and water under light, heat, the effect of water multi-environment factor were degraded Synergism, overcomes conventional single environment or multiple single environment factors are sequentially applied to coating surface and cause simulation difference Defect;Under the fine simulated marine atmosphere environment of no light condensation condition energy, coating evening is chronically under non-illuminated conditions simultaneously The effect of high humidity state.
The present invention by set up laboratory combine accelerated test and naval air environment test between reference coating aberration or The conversion coefficient of gloss loss, in the case that under accelerated test and naval air environment, coating aging mechanism is basically identical, adopts Under the identical solar radiation quantity of the equivalent assessment coating of laboratory accelerated test data, the aberration or gloss loss of ocean atmospheric experiment, accelerates Multiplying power is up to more than 8 times;Compared with atmospherical exposure test result, error is less than 15% to the assessment result of coating performance change.
Description of the drawings
The description of the drawings of the present invention is as follows:
Fig. 1 is composed for simulated marine atmosphere environmental accelerated test of the present invention;
Fig. 2 is multiple-factor Synergism Testing curve chart;
After Fig. 3 is the two kinds of experimental enviroment tests of TH52-85 epoxy zinc rich primer+TS55-80 polyurethane finish references coating Infrared spectrum;
Fig. 4 is the two kinds of experimental enviroment tests of TH52-97 epoxy zinc rich primer+TS04-98 polyurethane finishs coating to be assessed Infrared spectrum afterwards;
Fig. 5 is chromatic aberration curve chart after two kinds of coating tests;
Fig. 6 is equivalent appraisal procedure figure;
Fig. 7 is TH52-85 epoxy zinc rich primer+TS55-80 polyurethane finish reference coating aberration regression equations;
Regression curves of the Fig. 8 for TH52-85 epoxy zinc rich primer+TS55-80 polyurethane finish reference coatings.
Specific embodiment
Below in conjunction with the accompanying drawings the specific embodiment of the present invention is described in further detail, but invention is not limited to Present embodiment, any improvement or replacement on the present embodiment essence spirit still fall within the required guarantor of the claims in the present invention The scope of shield.
As described below is done to the test specimen that the present invention is selected below:
The present invention is using TH52-85 epoxy zinc rich primer+TS55-80 polyurethane finishs coatings as reference coating;Using TH52-97 epoxy zinc rich primer+TS04-98 polyurethane finishs coatings are used as coating to be assessed.
All samples size of the present invention is 150 × 50mm, build 110um~140um, with sandblasting cold-rolled steel sheet as base Material, then cleans substrate surface, finally sprays corresponding coating, spontaneously dries.
The method that the present invention is adopted does not require to carry out Natural Environmental Test, but adds to more preferably illustrate that this method is adopted The simulation of speed test and the accuracy of equivalent assessment, will also illustrate Natural Environmental Test method and result of the test below.
Embodiment 1:Natural environment atmospherical exposure test is opened in the Forests in Wanning, Hainan Islands experimental station with typical ocean atmospheric environment Exhibition, apart from 95 meters of coastline, model is tested to face south at test site, exposes with the horizontal 45° angle, and detection cycle is:1 month, 2 Individual month, 3 months, 6 months, 9 months, 12 months, the aberration of each cycle detection sample, glossiness and Fourier infrared spectrum.
The ring that laboratory accelerated test condition design plays a crucial role to coating aging in mainly considering naval air environment Border factor, major embodiment solar radiation, drying-moistening alternating, temperature cycles, humidity, salt fog and night condensation are to coating Fig. 1 is shown in comprehensive function, including multiple-factor Synergism Testing and salt spray test, its accelerated test Environmental Spectrum.
One test period test of the multiple-factor Synergism Testing includes 5 times circulating, totally 5 days, and each circulation time is 24h, using solar radiation, temperature cycles and moistening-drying, alternately three kinds of factors act synergistically on coating for circulation every time, then Coating is made to keep condensation, each experimental condition to see Fig. 2 in no light condition, wherein:
The solar radiation condition:It is 280nm~3000nm from wavelength, irradiance is 1120 ± 47w/m2Metal halogen Plain light shines, wherein, illumination 20h when circulating every time closes light source 4h.
The Thermal cycling conditions:8h high temperature:44 DEG C of illumination, 12h coolings:Under illumination condition, 44 DEG C drop to 34 DEG C, and 1h is low Temperature:34 DEG C unglazed, and 3h heats up, and under no light condition, 34 DEG C are raised to 44 DEG C, and the temperature cycle range ensure that sample temperature is less than Sample surface temperature extreme value under naval air environment, while meeting actual temperature fluctuation range, any of the above-described stage is relatively wet Degree is all higher than equal to 90%.
The moistening-be dried alternation condition:Carry out moistening under illumination condition-alternating action is dried, using air condensation Moistened, drying is realized in illumination, be the alternate cycles for moistening-being dried per 4h, moistening is 1 with the time scale being dried: 3,20h illumination moisten for 5 times totally-it is dried alternate cycles.Higher moistening-be dried alternating frequency can true simulated marine atmosphere environment Strong solar radiation, high temperature, sample surfaces thin liquid film change procedure caused by high humidity, reach sample quick aging purpose down.
The no light condition keeps condensation condition:No light time 4h, carries out condensation using air.The condition is mainly Under simulated marine atmosphere environment non-illuminated conditions of lower night, high humidity state is affected on coating aging.
The salt spray test condition be 35 DEG C of vapo(u)rizing temperature, 5% NaCl solution, dilute hydrochloric acid adjust to pH=4.5~ 5.5,24h is one cycle.
Simulated acceleration test spectrum as shown in Figure 1, is replaced using SC500 solar radiations proof box and simulation drying-condensation Acting device carries out multiple-factor collaboration son test, carries out salt fog test using FY-10E salt spray test chambers, altogether 6 circulation groups Test is closed, aberration, glossiness and the Fourier infrared spectrum of coating after each loop ends, is detected.
By infrared spectrum, aberration and illumination variation judge coating sample in accelerated test and marine atmosphere exposure test The concordance of agine mechaism and aging rule, sets up reference between laboratory combination accelerated test and naval air environment test and applies The conversion coefficient of layer aberration or gloss loss, using accelerated test aberration or gloss loss and reference coating aberration or gloss loss conversion system The coating aberration of ocean atmospheric experiment or gloss loss change under the identical solar radiation quantity of the equivalent assessment of several products.
Result of the test:
1. coating failure mechanism
Coating sample is exposed under naval air environment, and due to being acted on by intensive ultraviolet, in resin, strand is subject to Destruction, coating surface macromolecules degradation form volatile small molecule product and hydrophilic oxidation product, and hydrophilic oxidation product is molten Coating surface is left in water, finally causes the catabiosis such as coating efflorescence, discoloration, loss of gloss.Using Fourier infrared spectrum to reality The coating for testing room accelerated test and naval air environment test carries out molecular structure characterization and functional group's identification, sees Fig. 3~4, comments Sentence the concordance of coating aging mechanism under two kinds of environment.Can be seen by the original infrared spectrum of reference coating and coating to be assessed Go out, 1720cm-1, 1460cm-1, 1140cm-1Nearby peak is the characteristic absorption peak of two kinds of coated polyurethanes, wherein, 1750~ 1500cm-1Between be-NH-COO-, N-H and C-N absworption peak;1250~1000cm-1Between occur that C-O, C-N absorb Peak;1720cm-1It is nearby C=O characteristic absorption peaks;1020cm-1It is nearby the absworption peak of pigment (Talcum).Two kinds of environmental tests Afterwards, the 1722cm of TH52-85 epoxy zinc rich primers+TS55-80 polyurethane finish coatings-1And 1463cm-1Characteristic peak at position Significantly weaken, 1141cm-1Characteristic peak at position disappears;TH52-97 epoxy zinc rich primer+TS04-98 polyurethane finishs Coating change becomes apparent from, and all characteristic peaks disappear, further contrast characteristic peak and inorganic peak (1020cm-1) than value changes, can To find out, under two kinds of environment, the characteristic peak of each coating and inorganic p-ratio before the test after decline to a great extent, this explanation, two In kind of experimental enviroment, the agine mechaism of each coating is essentially identical, polyurethane macromolecular chain interruption, coating surface resin film forming matter by It is gradually aging.
2. coating aging rule
By taking reference coating aberration result as an example, using chart matching type, reference coating experiments room accelerated test and sea are passed judgment on The concordance of foreign atmospheric environment test aging rule, is shown in Fig. 5.Learnt by figure, reference coating experiments room accelerated test is big with ocean The chromatic aberration trend of gas environmental test is basically identical.
In sum, Changing Pattern of the coating under two kinds of experimental enviroments is consistent with failure mechanism, illustrates that the laboratory adds Speed test is with good simulation.
Coating aberration or gloss loss change assessment under naval air environment:
By taking aberration as an example, assessment TH52-97 epoxy zinc rich primer+TS04-98 polyurethane finishs coating ocean to be assessed is big The aberration of gas environmental test, step are as shown in Figure 6.
By carrying out the value of chromatism that coating to be assessed is obtained with reference coating identical laboratory accelerated test.
According to reference coating test data, the color of reference coating experiments room accelerated test and naval air environment test is set up Difference regression equation, is shown in Fig. 7, and regression curve is shown in Fig. 8, and simulation coefficient is 98%, more than 95%.
Obtain the aberration under coating experiments room to be assessed accelerated test solar radiation quantity identical with naval air environment test Value, if with 2700MJ/m2The value of chromatism under naval air environment is calculated as a example by solar radiation quantity.
2700MJ/m is calculated according to formula (1)2The conversion coefficient of reference coating, K=0.56 under solar radiation quantity.By formula (2) calculate 2700MJ/m2During solar radiation quantity, aberration Y=3.02 of the system to be assessed under naval air environment.
Verify coating value of chromatism (if necessary) to be assessed.Know that coating to be assessed exists by naval air environment test 2700MJ/m2Under solar radiation quantity, the measured value of ocean atmospheric environment test aberration is 2.98, compared with equivalent assessment result, by mistake Difference is 1.3%, much smaller than 15%.
Analyze by more than, laboratory accelerated test and naval air environment result of the test have preferable equivalence, can be with By the data of shorter laboratory accelerated test time Pre-Evaluation marine atmosphere exposure test, and error is less.

Claims (4)

1. it is a kind of simulation coating system naval air environment combination accelerated test method, it is characterised in that:Carry out successively many Factor Synergism Testing, salt spray test, and it is combined circulation;
The time of test cycle is 6 days, wherein, the multiple-factor Synergism Testing a cycle test period is 5 days, salt fog Test a cycle test period is 1 day;
The experimental condition of the salt spray test is:35 °C of vapo(u)rizing temperature, 5% NaCl solution, dilute hydrochloric acid adjust to pH=4.5~ 5.5;
Multiple-factor Synergism Testing a cycle test includes 5 circulations, every time circulation adopt solar radiation, temperature cycles and Alternately three kinds of factors act synergistically on coating system for moistening-drying, then make coating system keep condensation in no light condition;
Described each cycle period of multiple-factor Synergism Testing is 24h, wherein:
The solar radiation condition:0h is to 20h illumination, light source:1120±10% W/m2, 20h- 24h closing light sources;
The Thermal cycling conditions:0h is to 8h high temperature:44 DEG C of illumination, 8h to 20h coolings:Under illumination condition, 44 DEG C 34 DEG C are dropped to, 20h to 21h keeps 1h low temperature:34 DEG C are unglazed, and 21h to 24h carries out 3h intensifications, under no light condition, 34 DEG C 44 DEG C are raised to, any of the above-described stage relative humidity is all higher than equal to 90%;
The moistening-be dried alternation condition:Carry out moistening under illumination condition-alternating action is dried, carried out using air condensation Moistening, illumination realize drying, are the alternate cycles for moistening-being dried per 4h, and moistening is 1 with the time scale being dried:3, Moisten for totally 5 times under 20h illumination conditions-it is dried alternate cycles;
No light condition keeps condensation condition:In the no light time 4h of 20h to 24h, condensation is carried out using air.
2. it is a kind of simulation coating system naval air environment the equivalent appraisal procedure of combination accelerated test, initially with following Test method is tested, it is characterised in that:The test method is specially:
It is a kind of simulation coating system naval air environment combination accelerated test method, carry out successively multiple-factor Synergism Testing, Salt spray test, and it is combined circulation;
The time of test cycle is 6 days, wherein, the multiple-factor Synergism Testing a cycle test period is 5 days, salt fog Test a cycle test period is 1 day;
The experimental condition of the salt spray test is:35 °C of vapo(u)rizing temperature, 5% NaCl solution, dilute hydrochloric acid adjust to pH=4.5~ 5.5;
Multiple-factor Synergism Testing a cycle test includes 5 circulations, every time circulation adopt solar radiation, temperature cycles and Alternately three kinds of factors act synergistically on coating system for moistening-drying, then make coating system keep condensation in no light condition;
Described each cycle period of multiple-factor Synergism Testing is 24h, wherein:
The solar radiation condition:0h is to 20h illumination, light source:1120±10% W/m2, 20h- 24h closing light sources;
The Thermal cycling conditions:0h is to 8h high temperature:44 DEG C of illumination, 8h to 20h coolings:Under illumination condition, 44 DEG C 34 DEG C are dropped to, 20h to 21h keeps 1h low temperature:34 DEG C are unglazed, and 21h to 24h carries out 3h intensifications, under no light condition, 34 DEG C 44 DEG C are raised to, any of the above-described stage relative humidity is all higher than equal to 90%;
The moistening-be dried alternation condition:Carry out moistening under illumination condition-alternating action is dried, carried out using air condensation Moistening, illumination realize drying, are the alternate cycles for moistening-being dried per 4h, and moistening is 1 with the time scale being dried:3, Moisten for totally 5 times under 20h illumination conditions-it is dried alternate cycles;
No light condition keeps condensation condition:In the no light time 4h of 20h to 24h, condensation is carried out using air;
Equivalent appraisal procedure is:
After circulation composite test terminates every time, detection obtains coating system performance change data;
Determine reference coating system;
The reference coating system aberration set up under laboratory combination identical with the naval air environment solar radiation quantity of accelerated test or The conversion coefficient of gloss loss;
Using accelerated test aberration or gloss loss and the equivalent assessment of the product of reference coating system aberration or gloss loss conversion coefficient Coating aberration or gloss loss change under naval air environment.
3. combination accelerated test equivalent appraisal procedure of the coating system in naval air environment is simulated as claimed in claim 2, its It is characterised by:The conversion coefficient of the reference coating system aberration or gloss loss is when two kinds of experimental enviroment solar radiation quantities are identical When, reference coating system ratio in both environments between corresponding aberration or gloss loss, computational methods answer coincidence formula (1):
K=A/B (1)
In formula:
K --- reference coating system aberration or gloss loss conversion coefficient;
A --- the corresponding reference coating system aberration of experimental enviroment A or gloss loss value;
B --- the corresponding reference coating system aberration of experimental enviroment B or gloss loss value.
4. combination accelerated test equivalent appraisal procedure of the coating system in naval air environment is simulated as claimed in claim 2, its It is characterised by:The employing accelerated test aberration or gloss loss and reference coating system aberration or the product of gloss loss conversion coefficient Coincidence formula is answered in coating system aberration or gloss loss change under equivalent assessment naval air environment(2):
Y=K×X (2)
In formula:
The aberration or gloss loss Pre-Evaluation value of Y --- coating system marine atmosphere exposure test;
K --- reference coating system aberration or gloss loss conversion coefficient;
X --- specify under solar radiation quantity, combine the measured value of aberration or gloss loss in accelerated test.
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