CN107894387A

CN107894387A - A kind of method of whiteness measure of the change method detection sclerotin porcelain glaze paint resistance to chemical corrosion

Info

Publication number: CN107894387A
Application number: CN201711052234.0A
Authority: CN
Inventors: 李文杰; 许文超; 王博; 赵淑忠; 鲁学军; 郝秋伟; 李丽华
Original assignee: Individual
Current assignee: Individual
Priority date: 2017-11-01
Filing date: 2017-11-01
Publication date: 2018-04-10

Abstract

The invention discloses a kind of method of whiteness measure of the change method detection sclerotin porcelain glaze paint resistance to chemical corrosion, including sample preparation and pretreatment；Room temperature is tested；Heat run；Result of the test calculates；The data revision of the convention；The steps such as performance judgment；The present invention carries out precisely quantitative detection, and calculate its whiteness changes delta W value using spectrophotometric color measurement instrument to the sclerotin porcelain glaze paint resistance to chemical corrosion characterized with whiteness changes delta W；Present invention provide that after the chemical solution corrosion of variety classes, various concentrations, in the abrasion cycle of specified temp, measure Bone China sample is by the whiteness changes delta W before and after losing；With reference to internationally recognized color distortion decision criteria, realize to the corrosion proof accurate quantitative test of sclerotin porcelain glaze paint.The present invention improves the technical merit of Ceramic glaze resistance to chemical corrosion detection, reaches modernization and quantification, to realize that instrument and equipment hardware foundation has been established in the precision of testing result.

Description

A kind of whiteness measure of the change method detection sclerotin porcelain glaze paint resistance to chemical corrosion Method

Technical field

The present invention relates to sclerotin ceramic material and product glaze paint resistance to chemical corrosion quantitative measuring method, is specifically a kind of answer With spectrophotometric color measurement instrument to the detection method of the sclerotin porcelain glaze paint resistance to chemical corrosion characterized with whiteness changes delta W, belong to pottery Porcelain physicochemical property detection technique field..

Background technology

Most significant advantage is to cause after bone black is added in raw material in finished product containing suitable for the more traditional ordinary porcelain of Bone China The tricalcium phosphate of amount, domestic and international market is enjoyed to favor because of its " thin as a piece of paper, thoroughly such as mirror, sound such as single sonorous stone, white as a jade ".Porcelain body mainly by The multiphase material compositions such as crystalline phase, glass phase, gas phase, wherein phosphate glass mutually account for 16%~20%（Volume fraction）, play solid The effect of crystalline phase in porcelain is tied, because the optical property of its isotropy make it that porcelain body whiteness is higher.This high-grade porcelain due to Bone China There is larger difference in kind, its unique high temperature biscuiting, intermediate glaze on composition of raw materials and production technology compared with traditional ordinary porcelain The calcining system of burning so that relatively poor into ceramic glaze surface chemical stability.In daily life, when use Bone China meal, drink, kitchen When tool holds acidic food, glaze paint generally occurs within deep mixed flaw stain residual or color and luster reduction, causes porcelain use value big Give a discount, therefore its glaze paint resistance to chemical corrosion actually weighs a good and bad important indicator of product quality.

Glaze used in Bone China is fritted glaze, and its soda acid ratio is between 1:1~1:Between 3；Glazed thickness is usually 0.2~ 1.0mm, there is certain hardness and fragility, chemical composition is not fixed, and one layer of nature of glass for being equivalent to be attached to billet surface is consolidated Solution；Strong acid is insoluble in, to gas and liquid without osmosis.Acidic materials are mainly reflected in the corrosion mechanism of Ceramic glaze Glaze neutral and alkali composition is decomposed, makes Na⁺Ion is in free state, H⁺Ion penetrates into glaze layer according to Diffusion Law, although cation carries Body and corresponding electronics counteragent do not change, but glaze paint chemical composition has changed, corrosiveness of the acidic materials to glaze layer Start from (OH^-) group is replaced into (SiO^4-), when product is with (ONa^-) while occur, hydrone is adsorbed group's state again, meet Water decomposition effect constantly lasts up to the final complex compound Si of generation⁴⁺+ O^2- ₆H⁺ _8-xNa⁺X；When it inhales as anasarca with shortness of breath silicic acid and Na salt When attached, in view of the effect of water-soluble or diffusivity, etching reaction is hard to carry on, therefore silicic acid is gathered in vitreous surface and forms one layer Diaphragm.

Alkaline matter is different from acid to the erosion mechanism of Ceramic glaze, in SiO₂For in the glaze layer vitreum of main body, Si⁴⁺With [SiO₄]^4-Form is present；Although Si-O key is strong higher, after introducing alkaline matter, the key good general of each key of glaze paint is because of R²⁺Pole Change is acted on and weakened, and after alkali metal or alkaline earth metal cation capture in glaze layer " free oxygen ", Si-O-Si bridge chains break Split and dissolve, rate of dissolution can be by formula V=Ae^Q/RTRepresent.Because erosion of the alkaline matter to Ceramic glaze is started from (OH^-) Ion nearby generates adsorption layer, therefore the generation of this process will be hindered when other anions coexist；Relative to acid solution erosion Speech, alkali lye cause corrosion rate very fast because can not form diaphragm in Ceramic glaze.

At present, about domestic ceramics glaze paint chemical resistance in terms of assay method it is relatively unilateral, mainly have national standard GB/ T 5003-1999《The measure of domestic ceramics device glaze paint chemical resistance》、GB/T 7988-2013《Enamel for glassed steel alkali resistance is molten The measure of corrosion performance》、GB/T 7989-2013《The measure of the resistance to boiling acid of enamel for glassed steel and its steam corrosion performance》、GB 9988-1988《Enamel alkaline resistance properties method of testing》、GB/T 9989.1-2015《The measure part 1 of enamel resistance to chemical attack The measure of acid resistance at room temperature》、GB/T 9989.2-2015《The resistance to boiling acid of measure part 2 of enamel resistance to chemical attack, boiling Rise the measure of neutral liquid and its steam chemical erosion》、GB/T 9989.3-2015《The measure of enamel resistance to chemical attack the 3rd Divide the measure that resistance to etched with alkali solution is carried out with hexagon container》、GB/T 9989.4-2015《The measure of enamel resistance to chemical attack 4 parts carry out the measure of resistance to etched with alkali solution with hydrostatic column》、GB/T 9989.5-2015《The survey of enamel resistance to chemical attack The measure of fixed 5th part resistance to chemical attack in closed system》With GB/T 4738-2015《Domestic ceramics material is acidproof, alkaline-resisting Performance measurement method》；If being applied to sclerotin ceramic glaze surface chemical resistance measure, following improper part be present：

1. national standard GB/T 5003-1999 Method And Principle is sample directly by three kinds of ammonium chloride, potassium hydroxide and glacial acetic acid experiments The effect of solution, observed at ambient temperature after certain time corrodes and determine its degree corroded；The kind of experiment reagent Class is excessively single, and experiment condition is limited only to room temperature, certain gap be present with the real use state of domestic ceramic product, therefore It is difficult to embody the performance quality that Bone China bears the chemicals attack such as acidity, alkalescence, salt during routine use comprehensively；

2. national standard GB/T 4738-2015 regulations grind off sample glaze layer, the micro-boiling 1h in the concentrated sulfuric acid or 10% sodium hydroxide solution, meter The sample weight for the part that is not corroded and original sample weight are calculated, is detected suitable for ceramic material corrosion resisting property, but for ceramics Glaze paint resistance to chemical corrosion testing field does not possess scientific value and practical significance then；

3. national standard GB/T 9989.1-2015, GB/T 9989.2-2015, GB/T 9989.3-2015, GB/T 9989.4- 2015th, GB/T 9989.5-2015 series standards equally use ISO 28706-1 using translation method:2008、ISO 28706- 2:2008、ISO 28706-3:2008、ISO 28706-4:2008 and ISO 28706-5:2010 serial international standards, it is got the bid Quasi- Part I provides that the erosion time of the acidic materials such as room temperature citric acid, sulfuric acid is only 15min ± 30s, actually makes with ceramics It is inconsistent with situation, and be difficult to science in the short time and weigh sample corrosion resisting property；Remaining four partial content of standard respectively provide It is weightless by measuring its after the acid of certain temperature and concentration, alkali and neutral liquid persistently corrode certain time to Enamel samples The weight loss rate of unit of account area.GB/T 7988-2013 and GB/T 7989-2013 refer to ISO 28706-4 respectively:2008 With ISO 28706-2:2008 formulate and form, it is specified that sample is after alkali and acid effect, unit area total weight loss and year corrosion speed The computational methods of rate；GB 9988-1988 are similar with its.

External Correlative Standard System prevailing for the time being in force mainly includes following technical specification：

1. international standard

1.1 ISO 2733-1983《 Vitreous and porcelain enamels -- Apparatus for Testing with acid and neutral liquids and their vaporous vitreous enamels-use acid and neutral liquid And its steam carries out the device of corrosion resistant test》, it is specified that the relevant experiment of the resistance to boiling acid solution erosion performance of enamel glaze paint fills The technical requirements put；

1.2 ISO 28706-1:2008《Vitreous And Porcelain Enamels - Determination Of Resistance To Chemical Corrosion -Part 1:Determination Of Resistance To Enamel and enamel acid corrosion-resistant are surveyed under Chemical Corrosion By Acids At Room Temperature room temperature conditions Determine method》, it is specified that under 23 DEG C ± 3 DEG C of experimental condition, 100g/L citric acid solutions, 0.2mol/L sulfuric acid solution pair are used After enamel glaze paint corrosion 15min ± 30s, using the method for xerotripsis/wet rubbing experiment qualitative evaluation sample acid corrosion-resistant performance；

1.3 ISO 28706-2:2008《Determination of resistance to chemical corrosion by Boiling acids, neutral liquids and/or their vapor enamel and enamel are to boiling hydrochloric acid, neutral solution The judgement of body and its steam corrosion resisting property》, it is specified that citric acid solution through 64g/L（Boiling liquid phase）, 30% (mass fraction) Sulfuric acid solution（Boiling liquid phase）And the hydrochloric acid solution of 20% (mass fraction)（Gas phase）Continuous action is distinguished to enamel glaze paint After 2.5h, 18h and 7d, the method for determination sample unit area total weight loss or erosion rate；

1.4 ISO 28706-3:2008《Determination of resistance to chemical corrosion by The judgement of alkaline liquids using a hexagonal vessel enamel and enamel to akaline liquid corrosion resisting property （Use hexagon container determination method）》, it is specified that using hexagon container through 95 DEG C of standard wash agent solution and 40 DEG C~95 DEG C other alkaline solutions continuous action at least 24h is distinguished to enamel glaze paint（Or 168h）Afterwards, determination sample unit area is always lost The method of weight；

1.5 ISO 28706-4:2008《Determination of resistance to chemical corrosion by The judgement of alkaline liquids using a cylindrical vessel enamel and enamel to akaline liquid corrosion resisting property （Use hydrostatic column determination method）》, it is specified that using sodium hydroxide solution of the hydrostatic column through 0.1mol/L at 80 DEG C ± 1 DEG C test temperature under the conditions of to enamel glaze paint continuous action 24h after, determination sample unit area total weight loss or erosion rate Method；

1.6 ISO 28706-5:2010《incrimination of resistance to chemical corrosion - The Determination of resistance to chemical corrosion in closed systems of Part 5 are warded off The part of measure the 5th of porcelain resistance to chemical attack:The measure of resistance to chemical attack in closed system》Series standard is, it is specified that industry is warded off The method of testing of porcelain chemistry-resistant characteristic, enamel sample is placed in autoclave, the hydrochloric acid through 20% (mass fraction) is molten Liquid and 1mol/L sodium hydroxide solution are respectively under the conditions of 140 DEG C ± 1 DEG C and 80 DEG C ± 0.1 DEG C of test temperature, to enamel After sample persistently corrodes 24h ± 5min, the method for the weightless simultaneously unit of account area weight loss rate of measure.

The experimental principle of above-mentioned serial international standard is essentially identical with class standard with other, is after qualitative range estimation sample loses Glaze quality changes or quantitative test mass loss rate.

2. American Standard：

2.1 ASTM C 735-2004(2014)《 Standard Test Method for Acid Resistance of Ceramic Decorations on Returnable Beer and Beverage Glass Containers can make repeatedly The acid proof standard test method of ceramic decoration glaze paint on nature of glass beer and container for drink》, it is specified that use 11.5% （Mass fraction）HCl solution ceramics sample glaze paint 20min is corroded under 25 DEG C ± 5 DEG C of temperature conditionss, then determine its glaze The situation of change of face glossiness, technical requirements are relatively easy, unilateral；

2.2 ASTM C 777-2004(2009)《Standard Test Method for Sulfide Resistance of The standard test method that ceramic decoration halophile acts on Ceramic Decorations on Glass glass》Define room Under the conditions of temperature, Ceramic glaze resistance to 4%（Volume fraction）Acetic acid solution and saturation sodium sulfide solution erosion performance qualitative detection side Method；

2.3 ASTM C 1203-2004(2014)《Standard Test Method for Quantitative Determination of Alkali Resistance of a Ceramic-Glass Enamel glass-ceramic glaze layers are alkaline-resisting Property quantitative determination standard test method》Define under the conditions of 95 DEG C of test temperature, Ceramic glaze is through 10%（Mass fraction）Hydrogen After sodium hydroxide solution corrodes 2h, the detection method of mass loss rate is calculated；

2.4 ASTM C 676-2004(2009)《Standard Test Method for Detergent Resistance The detergent-resistant code test of ceramic decoration on of Ceramic Decorations on Glass Tableware dinner glasses Method》Define under 60 DEG C ± 2 DEG C of experiment condition, add faience glaze glassware through 5%（Mass fraction）Sodium pyrophosphate is molten After liquid corrodes 2h, the qualitative checking method of glaze paint presentation quality change；

2.5 ASTM C 614-2010(2011)《Standard Test Method for Alkali Resistance of The standard test method of the resistance to alkali corrosion of Porcelain Enamels industry porcelain enamel》Define at 96 DEG C ± 0.20 DEG C Experiment condition under, Ceramic glaze calculates the detection method of mass loss rate after 5g/L sodium pyrophosphate solution corrodes 6h；

2.6 ASTM C 283-2013《Standard Test Methods for Resistance of Porcelain The standard test method of the resistance to boiling acid corrosion of Enameled Utensils to Boiling Acid enamel ware》Define Under 104 DEG C of experiment condition, Ceramic glaze is through 6%（Mass fraction）Citric acid solution corrode 2.5h after, calculate mass loss speed The detection method of rate；

3. Europe superscript

3.1 BS EN 13310:2015《Kitchen Sinks-Functional Requirements And Test The functional requirement of Methods kitchen sinks and method of testing》Define through 10%（Volume fraction）Acetic acid solution, 5%（Quality Fraction）Sodium hydroxide solution, 70%（Volume fraction）Alcoholic solution, the liquor natrii hypochloritis containing 5% Active Chlorine, 1%（Quality Fraction）Methylene blue solution, 3.4g/l sodium chloride solution under the conditions of 23 DEG C ± 5 DEG C of test temperature, to porcelain kitchen After sink persistently corrodes 16h ± 0.25h, the situation of change of sample glaze surface state is estimated；

3.2 BS EN 14428:2015《Shower Enclosures-Functional Requirements And Test Methods shower house  functional requirements and method of testing》Define through 10%（Volume fraction）Acetic acid solution, 5%（Mass fraction） Sodium hydroxide solution, 70%（Volume fraction）Alcoholic solution, the liquor natrii hypochloritis containing 5% Active Chlorine, 1%（Mass fraction） Methylene blue solution under the conditions of 23 DEG C ± 5 DEG C of test temperature, after persistently corroding 2h ± 0.25h to shower house, estimate sample The situation of change of product glaze surface state；

3.3 BS EN 14688:2015《Sanitary appliances-Wash basins-Functional Requirements and test methods sanitary ware washbowl functional requirements and method of testing》Define through 10%（Body Fraction）Acetic acid solution, 5%（Mass fraction）Sodium hydroxide solution, 70%（Volume fraction）Alcoholic solution, containing 5% activity The liquor natrii hypochloritis of chlorine, 1%（Mass fraction）The examination at 23 DEG C ± 5 DEG C of methylene blue solution, 3.4g/l sodium chloride solution Test under temperature conditionss, after persistently corroding 2h ± 0.25h to porcelain kitchen sink, estimate the situation of change of sample glaze surface state；

4. Australian Standard

AS 1976:1992《Vitreous china for use in sanitary appliances vitreous china sanitary wares》 The glaze paint of sanitary ceramics sample is defined respectively through 10%（Volume fraction）Acetic acid solution and 10%（Volume fraction）Citric acid Solution persistently corrodes more than 16h, 50% at 100 DEG C ± 5 DEG C（Volume fraction）Hydrochloric acid solution persistently invaded at 18 DEG C ± 3 DEG C Erosion more than 48h, 50 g/L sodium hydroxide solution persistently corrode more than 0.5h, 0.15 g/L stearic acid at 60 DEG C ± 5 DEG C Sodium solution persistently corrodes more than 48h, 3% at 60 DEG C ± 5 DEG C（Volume fraction）Sulfuric acid solution persistently invaded at 100 DEG C ± 5 DEG C Lose more than 16h；Then the method estimated to sanitary ceramics glaze paint cosmetic variation situation.

In summary, at present the qualitative checking method on ceramic resistance to chemical corrosion substantially with after erosion outside sample glaze paint Based on the range estimation change of appearance quality, unit area weight loss rate and experiment after quantitative measuring method is then generally lost with ceramics sample Erosion rate in cycle is as glaze paint Evaluation of Corrosion Resistance index.Because chemical substance as defined in existing qualitative test method is to pottery The etching time of ceramic products generally in more than 24h, in longer time interval, only remembers judgement sample glaze paint color and luster with residual sense Change can influence unavoidably observation accuracy；Therefore the factor such as eyesight and observation condition by experimenter is influenceed, and is visually observed As a result larger error be present.And existing sizing technique is mass loss rate method of testing in Performance Evaluating Indexes selection etc. and sclerotin Larger difference be present between the mass property of porcelain, actual use value and consumer's focal point, sclerotin ceramic glaze surface can not be met Science and the applicability requirement of resistance to chemical corrosion detection technique.

The content of the invention

The technical problem to be solved in the present invention is to provide whiteness measure of the change to detect sclerotin porcelain glaze paint chemical resistance Can method, the present invention is using spectrophotometric color measurement instrument to the sclerotin porcelain glaze paint resistance to chemical corrosion that is characterized with whiteness changes delta W Precisely quantitative detection is carried out, can solve the problem that Bone China or even ceramic material and product glaze paint resistance to chemical corrosion are precisely quantitatively surveyed Why inscribe.

In order to solve the above technical problems, the technical solution adopted by the present invention is：

The method that whiteness measure of the change detects sclerotin porcelain glaze paint resistance to chemical corrosion, it is characterised in that using spectral photometric colour measuring Instrument carries out precisely quantitative detection to the sclerotin porcelain glaze paint resistance to chemical corrosion characterized with whiteness changes delta W, and specific steps are such as Under：

（1）Sample preparation and pretreatment

The quantity and specification of 1.1 Bone China samples

By same producer, same production batch, type, specification, size are identical, surface flawless, without fault, without illuminated, intact Glaze, it is pin-free the defects of sclerotin ceramic whiteware square position as test sample, 3 Bone China samples to be derived from different samples are used as one Group；Square position sample extraction should meet sample quantities requirement used in room temperature experiment and heat run；

The sample quantities and specification of 1.2 room temperatures experiment

For room temperature test method, sample quantities are 11 groups, and every group of sample is served only for a kind of erosion test of reagent, Mei Geshi The cut lengths of sample are (60 ± 3) mm × (60 ± 3) mm, and thickness is not more than 6mm；It is ensured that sample detected part be covered with glaze paint and Smooth, the area of flat part should be greater than the diameter of lid；

The sample quantities and specification of 1.3 heat runs

For heat run method, sample quantities are 8 groups, and every group of sample is served only for a kind of erosion test of reagent, each sample Cut lengths be (80 ± 4) mm × (80 ± 4) mm, thickness is not more than 6mm；

1.4 sample pre-treatments

Sample should fully be cleaned before experiment, first cleaned with neutral detergent, then done respectively with running water and distilled water flushing Only；Sample after cleaning is blotted with cleaning towel, is put into baking 60min in the drying box that temperature is 100 DEG C ± 5 DEG C, and will Sample after drying, which moves into, cools down more than 2h in silica gel drier；

（2）Room temperature is tested

Before 2.1 pairs of Bone China samples carry out chemical attack experiment, meeting standard QB/T 1503-2011 first《Domestic ceramics Measuring brightness method》Under defined experiment condition, instrument is calibrated using the ceramic standard white plate through assay approval, simultaneously The measurement pattern of spectrophotometric color measurement instrument is set as continuously measurement 3 times, seeks arithmetic mean of instantaneous value automatically；

2.2, according to shown in Fig. 1, choose five measurement points, wherein measuring point A position successively in the glaze paint to be measured of each sample For the geometric center of sample, measuring point B, C, D, E position are respectively four points of two catercorner lengths of sample square surface A little at；Measure and record the position of each measuring point；

2.3 determine tristimulus values X, Y, Z at five point positions of A, B, C, D, E using instrument respectively, take its arithmetic mean of instantaneous value Data are evenly distributed as what the sample bore glaze face color before chemical attack；

2.4 pipette 11 kinds of testing liquids listed in 3.0ml ± 0.3ml tables 1 with liquid-transfering gun, are added dropwise respectively in 11 groups of Bone Chinas In the glaze paint of sample, the chemical solution of specimen surface is smeared uniformly with L rods, and five measuring point positions of A, B, C, D, E are completely covered Put, then rapidly tip upside down on lid on sample, it is covered whole pilot region；

2.5 during whole experiment reagent action time and ambient temperature and humidity condition should meet the regulation of table 1, and meet to hide Light requirement；

The room temperature experiment chemical reagent of table 1 and experimental condition

2.6 remove lid every 2h ± 2min, rinse pilot region well with distilled water and are blotted with nitrogen free filter paper, repeat Above-mentioned 2.3 operating procedure, determine each Sample A, the tristimulus values at five point positions of B, C, D, E respectively using spectrophotometric color measurement instrument X、Y、Z；Taking its average value, the glaze face color after certain chemical reagent corrodes special time is evenly distributed data as the sample；

2.7 after solution at room temperature etching time meets 10h ± 10min, termination test；

（3）Heat run

Before 3.1 pairs of Bone China samples carry out heat run, the 2.1st~2.4 operating procedure in above-mentioned room temperature experiment is repeated, is used Spectrophotometric color measurement instrument determines each Sample A, tristimulus values X, Y, Z at five point positions of B, C, D, E respectively, takes its arithmetic mean of instantaneous value Data are evenly distributed as what the sample bore glaze face color before chemical attack；

3.2 heat run equipment therefors are flat circular reactor, and structure is shown in Fig. 2；Joint test device as illustrated, it will treat Test specimens are put into reaction container bottom, make its glaze paint region to be tested upward；

1000mL is met testing liquid as defined in table 2 by the interface injection reaction vessel of reflux condenser, making molten by 3.3 Liquid fully submerges sample；Reflux condenser is installed, with rubber stopper seal experimental rig；

The heat run chemical reagent of table 2 and experimental condition

3.4 are passed through cooling water, connect electric heating coil power supply, with thermometer measure test temperature, the mercury ball of thermometer should be at trying Test the position of solution level half；During whole experiment, solution temperature should meet table 2 and provide and keep constant, from Testing liquid reaches defined temperature range and starts timing；

3.5 during experiment, for the testing liquid in fluidized state, should control the gathering speed of condensate collector In 8mL/3min~10mL/3min；

3.6 stop heating once every 2h ± 2min, and after the testing liquid cooling in question response bottle, sample is gripped out with long handle, Then fully rinsed with distilled water and the moisture of specimen surface is blotted with filter paper；

3.7 determine each Sample A, tristimulus values X, Y, Z at five point positions of B, C, D, E using spectrophotometric color measurement instrument respectively；Take As the sample, the glaze face color after certain chemical reagent corrodes special time in a heated condition is evenly distributed its average value Data；

After 3.8 reach the test period as defined in table 2, stop heating and termination test；

（4）As a result calculate

Because spectrophotometric color measurement instrument can determine and directly read tristimulus values X, Y, Z, therefore Bone China sample is lost front and rear glaze paint The numerical value of whiteness change, is calculated using following equation；

By each group Bone China sample of spectrophotometric color measurement instrument measurement by data based on losing front and rear tristimulus values X, Y, Z, CIE is calculated 1976(L^*a^*b^*) chromaticity coordinate x, y, z and chromaticity index a in the colour space^*、b^*Numerical value, it is white in QB/T 1503 Spend formula and calculate each group Bone China sample through the front and rear whiteness changing value Δ W of different classes of, different temperatures chemical reagent erosion； Specific formula for calculation is as follows：

x=X/(X+Y+Z)…………………………………………………………………(1)

y=Y/(X+Y+Z)…………………………………………………………………(2)

a^*=500[(X/X_n)^1/3-(Y/Y_n)^1/3]…………………………………………………(3)

b^*=200[(Y/Y_n)^1/3-(Z/Z_n)^1/3]…………………………………………………(4)

By the tone angle formulas of GB/T 7921, i.e. formula（5）Calculate the hue angle h of Bone China sample_ab：

h_ab=arcctg(b^*/a^*)……………………………………………………………(5)

As 135 °≤h_abDuring 315 ° of ＜, by formula（6）Calculate the whiteness value of bluish white sample：

W=Y-250(x-x_n)+3(y-y_n)……………………………………………………(6)

Work as h_ab135 ° of ＜, h_abAt >=315 °, by formula（7）Calculate the whiteness value of yellowish-white sample：

W=Y+818(x-x_n)-1365(y-y_n)…………………………………………………(7)

By formula（8）Calculating Bone China sample bears the glaze paint whiteness changing value before and after chemical attack：

ΔW=W-W′……………………………………………………………………(8)

In formula:

X --- X values；

Y --- Y values；

Z --- Z values；

X, y --- chromaticity coordinate；

a^*、b^*--- uniform chromaticity index；

X_n、Y_n、Z_n--- the standard illuminants D of CIE 1964₆₅Tristimulus values；

X_n=94.81, Y_n=100.00, Z_n=107.32；

h_ab--- the hue angle of sample；

Δ W --- same Bone China sample is by the difference for losing front and rear whiteness calculated value；

Whiteness calculated value of W --- the same Bone China sample after by chemical attack；

Whiteness calculated value of W ' --- the same Bone China sample before by chemical attack；

（5）The data revision of the convention

The data revision of the convention of measurement result should meet GB/T 4739-2015《Domestic ceramics pigment colourity assay method》In the 8.1st~ 8.3 pertinent regulations, tristimulus values X, Y, Z of each sample are directly read by instrument, and the tristimulus values of every group of sample is respectively with this The arithmetic mean of instantaneous value of 3 sample tristimulus values of group represents, is accurate to one decimal place；The chromaticity coordinate result of calculation of sample is repaiied About to four after decimal point, the chromaticity index revision of the convention to 2 significant digits；Sample is by losing the front and rear whiteness result of calculation revision of the convention extremely One decimal place；

（6）Performance judgment

6.1 the determination of sclerotin ceramic glaze surface resistance to chemical corrosion evaluation index

Science and Regulatory requirements based on Performance evaluation criterion, for Bone China sample different experiments temperature condition Under, after different classes of, various concentrations chemical reagent continuous action certain time, the variation tendency of glaze paint whiteness is presented mutually not The characteristics of identical；In reference American Standard ASTM C 283-2013《Standard Test Methods for Resistance The code test of the resistance to boiling acid corrosion of of Porcelain Enameled Utensils to Boiling Acid enamel ware Method》On the basis of as defined in boiling acid liquid corrosion performance relevant evaluation resistance to enamel glaze paint；For two kinds of differences of room mild heat Test temperature condition, in every kind of acid, alkalescence and neutral chemical reagent in the lasting corrosion process of Bone China sample, choosing Glaze paint whiteness change absolute value is compared before bearing chemical erosion compared with it at interval of sample measured by 2h in specific period | Δ W | Maximum bears the evaluation index of this reagent chemical corrosion resistance as the sample；The resistance to reagent chemistry of every group of Bone China sample The evaluation index of corrosive nature is whiteness change absolute value after its 3 sample erosions | Δ W | the arithmetic mean of instantaneous value of maximum；

The judgment basis of 6.2 sclerotin ceramic glaze surface resistances to chemical corrosion

According to internationally recognized color change difference decision criteria:

The color change difference decision criteria of table 3

According to data analysis rule and Common criterion, following classification criterion is taken：

| Δ W |≤0.5 is that color is unchanged, and resistance to chemical corrosion is good；

1.5 >=| Δ W | ＞ 0.5 is color change unobvious, and resistance to chemical corrosion is general；

| Δ W | ＞ 1.5 is that color change is obvious, and resistance to chemical corrosion is poor；

The judgement of 6.3 every groups of Bone China sample glaze paint resistance to chemical corrosion evaluation results

3 samples of every group of difference Bone China sample are derived from after same chemical reagent persistently corrodes specific period, when some Sample whiteness change absolute value | Δ W | maximum be more than this group of sample whiteness change absolute value | Δ W | maximum arithmetic average Value 10% when；Need to extract one group of above-mentioned experimental procedure of sample repetition again；Two groups of Bone China samples are through this examination before and after calculating Each sample whiteness change absolute value after specific period is corroded in agent | Δ W | the arithmetic mean of instantaneous value of maximum, and if some sample is white Degree change absolute value | Δ W | maximum be more than this two groups of 6 sample whiteness change absolute values | Δ W | maximum arithmetic mean of instantaneous value 10%, then abandon it；Take remaining sample whiteness change absolute value | Δ W | the arithmetic mean of instantaneous value of maximum is as the batch Bone China The critical parameter of this resistance to chemical reagent erosion performance of sample, and evaluated according to the 6.2 performance judgments foundations provided.

When thermometric is not needed during the heat run, the thermometer hole of reaction bulb is sealed using rubber stopper.

During the heat run during Adjustment Tests solution, original solution in reaction bulb should be poured out as early as possible, it is to be tested Dismantled after device cooling and rinsed 1~2 time with running water, then fully rinsed with distilled water.

Using the present invention of above-mentioned technical proposal, compared with prior art, beneficial effect is：

（1）It is advanced：By applying modern precision instrument --- spectrophotometric color measurement instrument is used as the inspection of Ceramic glaze resistance to chemical corrosion Measurement equipment, Bone China sample is measured by front and rear distribution of color data are lost, and calculates its whiteness changes delta W value；Carry The advance of high detection technique is horizontal, reaches modernization and the quantification of the detection of Ceramic glaze chemical resistance, to realize Instrument and equipment hardware foundation has been established in the precision of testing result；

（2）It is scientific：Correlation for sclerotin ceramic glaze surface color feature and its with glaze paint physicochemical property, lost with sample front and rear The change of glaze face color is turned to Performance Evaluating Indexes, investigates same sample whiteness under different temperatures, different reagent conditions and changes Δ W fluctuation range, meets the real use state of Bone China and consumer is used for the focus of value, further carries The high science and applicability of detection method；

（3）It is normative：Test result is evaluated according to internationally recognized color distortion decision criteria, instrument calibration, calculating Formula etc. is with reference to relevant regulations in national standard GB/T 4739-2015 and rower QB/T 1503-2011；Provide used in heat run The performance requirement of the structural diagrams of device and its each part, specify that sample size, point position, experiment reagent, etching time, As a result calculating, performance evaluation etc. technology contents；

（4）It is quantitative：The physical quantity of sclerotin ceramic glaze surface chemical resistance can be objectively responded by introducing --- lost front and rear glaze paint The changes delta W of whiteness tristimulus values X, Y, the Z data measured according to instrument, utilizes formula meter as correlated performance evaluation index Calculation obtains whiteness value of each sample after different reagents, different temperatures, different time chemical attack, while limits testing result Data revision of the convention scope, the quantification of testing result can be realized；

（5）Accuracy：Use the spectral photometric colour measuring that automaticity is high, advanced technology is ripe to be counted as test equipment, choose three Bone China sample glaze paint whiteness change absolute value after same chemical reagent corrodes different time | Δ W | the arithmetic average of maximum Value is used as correlated performance evaluation index；And point position is uniformly distributed as far as possible, rationally increase measuring point quantity；And utilize standard substance The measuring brightness result of instrument is calibrated, can effectively avoid measurement error；

（6）It is innovative：Five measurement positions of specimen surface can ensure that measuring point be evenly distributed, reasonable quantity；Examination is used as using its average Sample glaze paint distribution of color data, improve the accuracy and representativeness of testing result；2h ± 2min measurement frequency enhancing after erosion To the corrosion proof comprehensive assessment of sample, every group of sample glaze paint whiteness change absolute value is chosen | Δ W | the arithmetic average of maximum Value is used as Performance Evaluating Indexes；Conventional method is breached without clear and definite measuring point, the limitation without test loop；

（7）Operability：Spectrophotometric color measurement instrument is cheap, is widely used, and specimen size is easy to process as defined in the inventive method, Sample pre-treatments and a series of experiments are easy to operation；As a result calculation formula is simple and practical, and most of instruments can at present It is automatically performed the direct measurement of whiteness；Method is clear and specific to the description about experimental procedure items technical requirements, is easy to manage Solution and grasp, implementation process possess stronger operability；

（8）Universality：Based on above-mentioned advantage, the inventive method possesses stronger practicality, is advantageous to expand and is examining, learn, grind, producing The popularization and application of all circles；Be advantageous to support sclerotin ceramic material and product glaze paint resistance to chemical corrosion detection technique to realize pervasive Change, glaze paint resistance to chemical corrosion detection technique research that can be to other kinds of ceramic product provides reference.

Brief description of the drawings

Fig. 1 is the point position schematic diagram of sample glaze paint to be measured in the present invention；

In figure：A. at the geometric center on sample surface to be measured；B. the geometric center of sample and the midpoint of its right vertices line； C. the geometric center of sample and the midpoint of its left upper apex line；D. in the geometric center of sample and its bottom left vertex line At point；E. the geometric center of sample and the midpoint of its bottom right vertex line；

Fig. 2 is the structural representation of the flat circular reactor of heat run equipment therefor of the present invention；

In figure：1. nitrogen tube；2. water inlet；3. reflux condenser；4. temperature inductor；5. reaction vessel；6. electric heating coil；7. go out The mouth of a river；8. thermometer.

Embodiment

Below in conjunction with the accompanying drawings and preferred embodiment the present invention will be described in detail so that advantages and features of the invention energy It is easier to be readily appreciated by one skilled in the art, apparent is clearly defined so as to be made to protection scope of the present invention.

The present embodiment is said by taking the detection to the glaze paint resistance to chemical corrosion of " Tangshan Bone China " geography symbol product as an example It is bright.

Specific detection method is carried out in the steps below：

（1）Sample preparation and pretreatment

The quantity and specification of 1.1 Bone China samples

By same producer, same production batch, type, specification, size are identical, surface flawless, without fault, without illuminated, intact Glaze, it is pin-free the defects of sclerotin ceramic whiteware square position as test sample, 3 Bone China samples to be derived from different samples are used as one Group；Square position sample extraction should meet sample quantities requirement used in room temperature experiment and heat run.

The sample quantities and specification of 1.2 room temperatures experiment

For room temperature test method, sample quantities are 11 groups, and every group of sample is served only for a kind of erosion test of reagent, Mei Geshi The cut lengths of sample are (60 ± 3) mm × (60 ± 3) mm, and thickness is not more than 6mm；It is ensured that sample detected part be covered with glaze paint and Smooth, the area of flat part should be greater than the diameter of lid.

The sample quantities and specification of 1.3 heat runs

For heat run method, sample quantities are 8 groups, and every group of sample is served only for a kind of erosion test of reagent, each sample Cut lengths be (80 ± 4) mm × (80 ± 4) mm, thickness is not more than 6mm.

1.4 sample pre-treatments

Sample should fully be cleaned before experiment, first cleaned with neutral detergent, then done respectively with running water and distilled water flushing Only.Sample after cleaning is blotted with cleaning towel, is put into baking 60min in the drying box that temperature is 100 DEG C ± 5 DEG C, and will Sample after drying, which moves into, cools down more than 2h in silica gel drier.

（2）Room temperature is tested

Before 2.1 pairs of Bone China samples carry out chemical attack experiment, meeting standard QB/T 1503-2011 first《Domestic ceramics Measuring brightness method》Under defined experiment condition, instrument is calibrated using the ceramic standard white plate through assay approval, simultaneously The measurement pattern of spectrophotometric color measurement instrument is set as continuously measurement 3 times, seeks arithmetic mean of instantaneous value automatically.

2.2 according to shown in Fig. 1, choosing five measurement points successively in the glaze paint to be measured of each sample, wherein measuring point A's Position is the geometric center of sample, and measuring point B, C, D, E position are respectively two catercorner lengths of the sample square surface At a quarter point；Measure and record the position of each measuring point.

2.3 determine tristimulus values X, Y, Z at five point positions of A, B, C, D, E using instrument respectively, take its arithmetic to put down Average is evenly distributed data as what the sample bore glaze face color before chemical attack.

2.4 pipette 11 kinds of testing liquids listed in 3.0ml ± 0.3ml tables 1 with liquid-transfering gun, are added dropwise respectively in 11 groups of bones In the glaze paint of matter porcelain sample, the chemical solution of specimen surface is smeared uniformly with L rods, and five surveys of A, B, C, D, E are completely covered Point position, then lid is tipped upside down on sample rapidly, it is covered whole pilot region.

2.5 during whole experiment reagent action time and ambient temperature and humidity condition should meet the regulation of table 1, it is and full Sufficient shading requirement.

2.6 remove lid every 2h ± 2min, rinse pilot region well with distilled water and are blotted with nitrogen free filter paper, repeat Above-mentioned 2.3 operating procedure, determine each Sample A, the tristimulus values at five point positions of B, C, D, E respectively using spectrophotometric color measurement instrument X、Y、Z；Taking its average value, the glaze face color after certain chemical reagent corrodes special time is evenly distributed data as the sample.

2.7 after solution at room temperature etching time meets 10h ± 10min, termination test.

（3）Heat run

Before 3.1 pairs of Bone China samples carry out heat run, the 2.1st~2.4 operating procedure in above-mentioned room temperature experiment is repeated, is used Spectrophotometric color measurement instrument determines each Sample A, tristimulus values X, Y, Z at five point positions of B, C, D, E respectively, takes its arithmetic mean of instantaneous value Data are evenly distributed as what the sample bore glaze face color before chemical attack.

3.2 heat run equipment therefors are flat circular reactor, and structure is shown in Fig. 2；Joint test device as illustrated, Sample to be tested is put into reaction container bottom, makes its glaze paint region to be tested upward.

1000mL is met testing liquid as defined in table 2 by 3.3 to be injected in reaction vessel by the interface of reflux condenser, Solution is set fully to submerge sample；Reflux condenser is installed, with rubber stopper seal experimental rig.

The heat run chemical reagent of table 2 and experimental condition

3.4 are passed through cooling water, connect electric heating coil power supply, with thermometer measure test temperature, the mercury ball of thermometer should be at trying Test the position of solution level half.During whole experiment, solution temperature should meet table 2 and provide and keep constant, from Testing liquid reaches defined temperature range and starts timing.

3.5 during experiment, should be by the gathering speed of condensate collector for the testing liquid in fluidized state Control is in 8mL/3min~10mL/3min.

3.6 stop heating once every 2h ± 2min, after the testing liquid cooling in question response bottle, are gripped out with long handle Sample, then fully rinsed with distilled water and the moisture of specimen surface is blotted with filter paper.

3.7 determined respectively using spectrophotometric color measurement instrument each Sample A, tristimulus values X, Y at five point positions of B, C, D, E, Z；Taking its average value, the glaze face color after certain chemical reagent corrodes special time in a heated condition is averaged as the sample Distributed data.

After 3.8 reach the test period as defined in table 2, stop heating and termination test.

When thermometric is not needed during heat run, the thermometer hole of reaction bulb is sealed using rubber stopper.

Original solution in reaction bulb should be poured out as early as possible during heat run, be dismantled simultaneously after device cooling to be tested Rinsed 1~2 time with running water, then fully rinsed with distilled water.

（4）As a result calculate

Because spectrophotometric color measurement instrument can determine and directly read tristimulus values X, Y, Z, therefore Bone China sample is lost front and rear glaze paint The numerical value of whiteness change, is calculated using following equation.

By each group Bone China sample of spectrophotometric color measurement instrument measurement by data based on losing front and rear tristimulus values X, Y, Z, meter Calculate (the L of CIE 1976^*a^*b^*) chromaticity coordinate x, y, z and chromaticity index a in the colour space^*、b^*Numerical value, according to QB/T 1503 In whiteness formulas calculate each group Bone China sample and corrode front and rear whiteness through different classes of, different temperatures chemical reagent and change It is worth Δ W.Specific formula for calculation is as follows：

In formula:

X --- X values；

Y --- Y values；

Z --- Z values；

X, y --- chromaticity coordinate；

a^*、b^*--- uniform chromaticity index；

X_n=94.81, Y_n=100.00, Z_n=107.32；

h_ab--- the hue angle h of sample_ab；

Whiteness calculated value of W ' --- the same Bone China sample before by chemical attack.

（5）The data revision of the convention

The data revision of the convention of measurement result should meet GB/T 4739-2015《Domestic ceramics pigment colourity assay method》In the 8.1st~ 8.3 pertinent regulations, tristimulus values X, Y, Z of each sample are directly read by instrument, and the tristimulus values of every group of sample is respectively with this The arithmetic mean of instantaneous value of 3 sample tristimulus values of group represents, is accurate to one decimal place；The chromaticity coordinate result of calculation of sample is repaiied About to four after decimal point, the chromaticity index revision of the convention to 2 significant digits；Sample is by losing the front and rear whiteness result of calculation revision of the convention extremely One decimal place.

（6）Performance judgment

The determination of 6.1 sclerotin ceramic glaze surface resistance to chemical corrosion evaluation indexes

Science and Regulatory requirements based on Performance evaluation criterion, for Bone China sample different experiments temperature condition Under, after different classes of, various concentrations chemical reagent continuous action certain time, the variation tendency of glaze paint whiteness is presented mutually not The characteristics of identical；In reference American Standard ASTM C 283-2013《Standard Test Methods for Resistance The code test of the resistance to boiling acid corrosion of of Porcelain Enameled Utensils to Boiling Acid enamel ware Method》On the basis of as defined in boiling acid liquid corrosion performance relevant evaluation resistance to enamel glaze paint；For two kinds of differences of room mild heat Test temperature condition, in every kind of acid, alkalescence and neutral chemical reagent in the lasting corrosion process of Bone China sample, choosing Glaze paint whiteness change absolute value is compared before bearing chemical erosion compared with it at interval of sample measured by 2h in specific period | Δ W | Maximum bears the evaluation index of this reagent chemical corrosion resistance as the sample；The resistance to reagent chemistry of every group of Bone China sample The evaluation index of corrosive nature is whiteness change absolute value after its 3 sample erosions | Δ W | the arithmetic mean of instantaneous value of maximum.

The color change difference decision criteria of table 3

Feel the difference degree of color	\|ΔW\|
		Slightly	0~0.5
It is less	0.5~1.5
		Substantially	1.5~3.0
Clearly	3.0~6.0
		Significantly	6.0~12.0
It is extremely notable	More than 12.0

| Δ W | ＞ 1.5 is that color change is obvious, and resistance to chemical corrosion is poor.

3 samples of every group of difference Bone China sample are derived from after same chemical reagent persistently corrodes specific period, when some Sample whiteness change absolute value | Δ W | maximum be more than this group of sample whiteness change absolute value | Δ W | maximum arithmetic average Value 10% when；Need to extract one group of above-mentioned experimental procedure of sample repetition again.Two groups of Bone China samples are through this examination before and after calculating Each sample whiteness change absolute value after specific period is corroded in agent | Δ W | the arithmetic mean of instantaneous value of maximum, and if some sample is white Degree change absolute value | Δ W | maximum be more than this two groups of 6 sample whiteness change absolute values | Δ W | maximum arithmetic mean of instantaneous value 10%, then abandon it；Take remaining sample whiteness change absolute value | Δ W | the arithmetic mean of instantaneous value of maximum is as the batch Bone China The critical parameter of this resistance to chemical reagent erosion performance of sample, and evaluated according to the 6.2 performance judgments foundations provided.

Test reagent, test equipment, heat run device used in the present embodiment：

（1）Test reagent

Test water only uses distilled water or deionized water（Meet the tertiary effluent requirements of GB/T 6682）.

1.1 citric acid solutions, the citric acid monohydrate crystal for preparing solution should meet GB/T 8269 regulation.

1.2 acetic acid solutions, the acetic acid for preparing solution should meet GB/T 676 regulation.

1.3 hydrochloric acid solutions, the hydrochloric acid for preparing solution should meet GB/T 622 regulation.

1.4 sulfuric acid solutions, the sulfuric acid for preparing solution should meet GB/T 625 regulation.

1.5 sodium hydroxide solutions, the sodium hydroxide powder for preparing solution should meet GB/T 629 regulation.

1.6 sodium carbonate liquors, the natrium carbonicum calcinatum powder for preparing solution should meet GB/T 639 regulation.

1.7 sodium tripolyphosphate solution, Na in the sodium tripolyphosphate powder for preparing solution₅P₃O₁₀Content be not less than 90%.

1.8 liquor natrii hypochloritises, effective chlorine are not less than 5%（Mass fraction）.

1.9 sodium chloride solutions, the sodium chloride powder for preparing solution should meet GB/T 1266 regulation.

1.10 ethanol solutions, the absolute ethyl alcohol for preparing solution should meet GB/T 678 regulation.

1.11 sodium pyrophosphate solutions, the sodium pyrophosphate powder for preparing solution should meet HG/T 2968 regulation.

1.12 sodium stearate solutions are pure to analyze for preparing the odium stearate powder of solution.

（2）Test equipment and equipment

2.1 slide measure：Precision is ± 0.02mm.

2.2 micrometer：Precision is ± 0.01mm.

2.3 electric drying oven with forced convection：Temperature range is 0 DEG C~150 DEG C, and temperature-control range is ± 5 DEG C.

2.4 thermometers, range are 50 DEG C~100 DEG C, and scale division value is 0.2 DEG C.

2.5 time set：Precision is 1 min.

2.6 drier：Internal diameter is more than 200 mm.

2.7 balances, precision are 0.2 mg.

2.8 liquid-transfering guns, range are 1mL~5mL single track adjustable pipette；It is according to JJG 646 regulation verification result It is qualified.

2.9 L rods.

The surface plate of 2.10 lids, internal diameter about 90mm, polyethylene or glass material.

2.11 towel：White cotton products or lingerie.

2.12 filter paper：Floride-free compound.

2.13 long spindle clamp.

2.14 spectrophotometric color measurement instrument：Standard colorimetric system and International Commission on Illumination (CIE) D65 are supplemented using CIE 1964 Standard illuminants, technical conditions meet GB/T 3979-2008《The measuring method of object color》Regulation；Based on D₆₅Working flare, 2 ° The measuring condition and d/0 of standard colorimetric observer（Include specular reflection component SCI）Geometrical condition and 24 DEG C, 43%RH Instrument calibration environmental condition, in 380nm~780nm visible photo measure wave-length coverage（Measure wavelength interval 10nm）, whiteness The repdocutbility of measure is Δ I (Y)=0.06, Δ I (x)=0.0000, Δ I (y)=0.0000；Repeatability for s (Y)=0.01, s (x)= 0.0000, s (y)=0.0000；Stability is Δ Y=0.01；The repeatability standard deviation value of measuring brightness is less than 0.06；It is uncertain Spend for U (Y)=3.7 (k=2).

2.15 integrating sphere size：Φ40mm.

2.16 standard white plate：Meet GB/T 9086-2007《For colourity and the standard white plate of photometric measurement》It is defined Ceramic color standard material；Based on D₆₅Working flare, 10 ° of standard colorimetric observers, 0/d exclude mirror-reflection SCE measuring condition And 24 DEG C, 53%RH calibrating environmental condition.In 380nm~780nm visible photo measure wave-length coverage, certified value be X= 82.04, Y=86.75, Z=91.31, R457=85.36；Uncertainty is U (Y)=1.2 (k=2)；U (x), U (y)=0.0032, (k= 2)。

（3）Heat run device（As shown in Figure 2）：

3.1 condensate collectors, condensate collector, which is used to collect by the experimental liquid after condensing tube condensation, precision, is 0.1ml, 3.3 borosilicate glasses are made as defined in meeting ISO 3585.

3.2 condenser pipes, meet the spherical condensation tube with beam ground as defined in GB/T 28212, its heat exchanging part length More than 400mm, the borosilicate glass as defined in meeting ISO 3585 is made；Make chemical solution will not under the conditions of long term high temperature Lost because of evaporation.

3.3 temperature sensors, temperature-controlled precision are not more than 0.2 DEG C.

3.4 flat reaction vessels, the borosilicate glass required by meeting ISO 3585 are made, and volume is not less than 2000mL, end face is smooth, and bottleneck size is more than test sample size.Thermal shock test is carried out by GB/T 6579 requirement When, reaction vessel should be at least through 120 DEG C of the temperature difference sudden turn of events without destroying.

3.5 electric heating coils, it is made up of the alloy material outer wrapping insulation material with high thermal conductivity coefficient, table 2 can be reached and advised Fixed temperature requirement；It is installed on outside reaction vessel.

3.6 rubber stoppers, it is made up of the hardness being determined according to ISO 48 of 70IRHD synthetic rubber.The material should be able to be resistance to 100 DEG C of alkaline solution and 140 DEG C of citric acid and water (such as chlorobutadiene or second propylene）.

The detection data and result of the present embodiment calculate：

（1）Room temperature testing inspection data and it the results are shown in Table 4.

The room temperature testing inspection data of table 4 and result computational chart

（2）Heat run detects data and the results are shown in Table 5.

The heat run of table 5 detects data and result computational chart

The Bone China sample glaze paint resistance to chemical corrosion evaluation result of the present embodiment is shown in Table 6.

The Bone China sample glaze paint resistance to chemical corrosion evaluation result of table 6

Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to be said using the present invention The equivalent transformation that bright book and accompanying drawing content are made, or other related technical areas are directly or indirectly used in, it is included in this In the scope of patent protection of invention.

Claims

A kind of 1. method of whiteness measure of the change method detection sclerotin porcelain glaze paint resistance to chemical corrosion, it is characterised in that application Spectrophotometric color measurement instrument carries out precisely quantitative detection, tool to the sclerotin porcelain glaze paint resistance to chemical corrosion characterized with whiteness changes delta W Body step is as follows：

（1）Sample preparation and pretreatment

The quantity and specification of 1.1 Bone China samples

By same producer, same production batch, type, specification, size are identical, surface flawless, without fault, without illuminated, intact Glaze, it is pin-free the defects of sclerotin ceramic whiteware square position as test sample, 3 Bone China samples to be derived from different samples are used as one Group；Square position sample extraction should meet sample quantities requirement used in room temperature experiment and heat run；

The sample quantities and specification of 1.2 room temperatures experiment

For room temperature test method, sample quantities are 11 groups, and every group of sample is served only for a kind of erosion test of reagent, Mei Geshi The cut lengths of sample are (60 ± 3) mm × (60 ± 3) mm, and thickness is not more than 6mm；It is ensured that sample detected part be covered with glaze paint and Smooth, the area of flat part should be greater than the diameter of lid；

The sample quantities and specification of 1.3 heat runs

For heat run method, sample quantities are 8 groups, and every group of sample is served only for a kind of erosion test of reagent, each sample Cut lengths be (80 ± 4) mm × (80 ± 4) mm, thickness is not more than 6mm；

1.4 sample pre-treatments

Sample should fully be cleaned before experiment, first cleaned with neutral detergent, then done respectively with running water and distilled water flushing Only；Sample after cleaning is blotted with cleaning towel, is put into baking 60min in the drying box that temperature is 100 DEG C ± 5 DEG C, and will Sample after drying, which moves into, cools down more than 2h in silica gel drier；

（2）Room temperature is tested

Before 2.1 pairs of Bone China samples carry out chemical attack experiment, meeting standard QB/T1503-2011 first《Domestic ceramics is white Spend assay method》Under defined experiment condition, instrument is calibrated using the ceramic standard white plate through assay approval, simultaneously will The measurement pattern of spectrophotometric color measurement instrument is set as continuously measurement 3 times, seeks arithmetic mean of instantaneous value automatically；

2.2, according to shown in Fig. 1, choose five measurement points successively in the glaze paint to be measured of each sample, and wherein measuring point A position is The geometric center of sample, measuring point B, C, D, E position be respectively two catercorner lengths of sample square surface four/ At a bit；Measure and record the position of each measuring point；

2.3 determine tristimulus values X, Y, Z at five point positions of A, B, C, D, E using instrument respectively, take its arithmetic mean of instantaneous value Data are evenly distributed as what the sample bore glaze face color before chemical attack；

2.4 pipette 11 kinds of testing liquids listed in 3.0ml ± 0.3ml tables 1 with liquid-transfering gun, are added dropwise respectively in 11 groups of Bone Chinas In the glaze paint of sample, the chemical solution of specimen surface is smeared uniformly with L rods, and five measuring point positions of A, B, C, D, E are completely covered Put, then rapidly tip upside down on lid on sample, it is covered whole pilot region；

2.5 during whole experiment reagent action time and ambient temperature and humidity condition should meet the regulation of table 1, and meet to hide Light requirement；

The room temperature experiment chemical reagent of table 1 and experimental condition

2.6 remove lid every 2h ± 2min, rinse pilot region well with distilled water and are blotted with nitrogen free filter paper, repeat Above-mentioned 2.3 operating procedure, determine each Sample A, the tristimulus values at five point positions of B, C, D, E respectively using spectrophotometric color measurement instrument X、Y、Z；Taking its average value, the glaze face color after certain chemical reagent corrodes special time is evenly distributed data as the sample；

2.7 after solution at room temperature etching time meets 10h ± 10min, termination test；

（3）Heat run

Before 3.1 pairs of Bone China samples carry out heat run, the 2.1st~2.4 operating procedure in above-mentioned room temperature experiment is repeated, is used Spectrophotometric color measurement instrument determines each Sample A, tristimulus values X, Y, Z at five point positions of B, C, D, E respectively, takes its arithmetic mean of instantaneous value Data are evenly distributed as what the sample bore glaze face color before chemical attack；

3.2 heat run equipment therefors are flat circular reactor, and structure is shown in Fig. 2；Joint test device as illustrated, it will treat Test specimens are put into reaction container bottom, make its glaze paint region to be tested upward；

1000mL is met testing liquid as defined in table 2 by the interface injection reaction vessel of reflux condenser, making molten by 3.3 Liquid fully submerges sample；Reflux condenser is installed, with rubber stopper seal experimental rig；

The heat run chemical reagent of table 2 and experimental condition

3.4 are passed through cooling water, connect electric heating coil power supply, with thermometer measure test temperature, the mercury ball of thermometer should be at trying Test the position of solution level half；During whole experiment, solution temperature should meet table 2 and provide and keep constant, from Testing liquid reaches defined temperature range and starts timing；

3.5 during experiment, for the testing liquid in fluidized state, should control the gathering speed of condensate collector In 8mL/3min~10mL/3min；

3.6 stop heating once every 2h ± 2min, and after the testing liquid cooling in question response bottle, sample is gripped out with long handle, Then fully rinsed with distilled water and the moisture of specimen surface is blotted with filter paper；

3.7 determine each Sample A, tristimulus values X, Y, Z at five point positions of B, C, D, E using spectrophotometric color measurement instrument respectively；Take As the sample, the glaze face color after certain chemical reagent corrodes special time in a heated condition is evenly distributed its average value Data；

After 3.8 reach the test period as defined in table 2, stop heating and termination test；

（4）As a result calculate

Because spectrophotometric color measurement instrument can determine and directly read tristimulus values X, Y, Z, therefore Bone China sample is lost front and rear glaze paint The numerical value of whiteness change, is calculated using following equation；

By each group Bone China sample of spectrophotometric color measurement instrument measurement by data based on losing front and rear tristimulus values X, Y, Z, CIE is calculated 1976(L^*a^*b^*) chromaticity coordinate x, y, z and chromaticity index a in the colour space^*、b^*Numerical value, it is white in QB/T 1503 Spend formula and calculate each group Bone China sample through the front and rear whiteness changing value Δ W of different classes of, different temperatures chemical reagent erosion； Specific formula for calculation is as follows：

x=X/(X+Y+Z)…………………………………………………………………(1)

y=Y/(X+Y+Z)…………………………………………………………………(2)

a^*=500[(X/X_n)^1/3-(Y/Y_n)^1/3]…………………………………………………(3)

b^*=200[(Y/Y_n)^1/3-(Z/Z_n)^1/3]…………………………………………………(4)

By the tone angle formulas of GB/T 7921, i.e. formula（5）Calculate the hue angle h of Bone China sample_ab：

h_ab=arcctg(b^*/a^*)……………………………………………………………(5)

As 135 °≤h_abDuring 315 ° of ＜, by formula（6）Calculate the whiteness value of bluish white sample：

W=Y-250(x-x_n)+3(y-y_n)……………………………………………………(6)

Work as h_ab135 ° of ＜, h_abAt >=315 °, by formula（7）Calculate the whiteness value of yellowish-white sample：

W=Y+818(x-x_n)-1365(y-y_n)…………………………………………………(7)

By formula（8）Calculating Bone China sample bears the glaze paint whiteness changing value before and after chemical attack：

ΔW=W-W′……………………………………………………………………(8)

In formula:

X --- X values；

Y --- Y values；

Z --- Z values；

X, y --- chromaticity coordinate；

a^*、b^*--- uniform chromaticity index；

X_n、Y_n、Z_n--- the standard illuminants D of CIE 1964₆₅Tristimulus values；

X_n=94.81, Y_n=100.00, Z_n=107.32；

h_ab--- the hue angle of sample；

Δ W --- same Bone China sample is by the difference for losing front and rear whiteness calculated value；

Whiteness calculated value of W --- the same Bone China sample after by chemical attack；

Whiteness calculated value of W ' --- the same Bone China sample before by chemical attack；

（5）The data revision of the convention

The data revision of the convention of measurement result should meet GB/T 4739-2015《Domestic ceramics pigment colourity assay method》In the 8.1st~ 8.3 pertinent regulations, tristimulus values X, Y, Z of each sample are directly read by instrument, and the tristimulus values of every group of sample is respectively with this The arithmetic mean of instantaneous value of 3 sample tristimulus values of group represents, is accurate to one decimal place；The chromaticity coordinate result of calculation of sample is repaiied About to four after decimal point, the chromaticity index revision of the convention to 2 significant digits；Sample is by losing the front and rear whiteness result of calculation revision of the convention extremely One decimal place；

（6）Performance judgment

The determination of 6.1 sclerotin ceramic glaze surface resistance to chemical corrosion evaluation indexes

Science and Regulatory requirements based on Performance evaluation criterion, for Bone China sample different experiments temperature condition Under, after different classes of, various concentrations chemical reagent continuous action certain time, the variation tendency of glaze paint whiteness is presented mutually not The characteristics of identical；In reference American Standard ASTM C 283-2013《Standard Test Methods for Resistance The code test of the resistance to boiling acid corrosion of of Porcelain Enameled Utensils to Boiling Acid enamel ware Method》On the basis of as defined in boiling acid liquid corrosion performance relevant evaluation resistance to enamel glaze paint；For two kinds of differences of room mild heat Test temperature condition, in every kind of acid, alkalescence and neutral chemical reagent in the lasting corrosion process of Bone China sample, choosing Glaze paint whiteness change absolute value is compared before bearing chemical erosion compared with it at interval of sample measured by 2h in specific period | Δ W | Maximum bears the evaluation index of this reagent chemical corrosion resistance as the sample；The resistance to reagent chemistry of every group of Bone China sample The evaluation index of corrosive nature is whiteness change absolute value after its 3 sample erosions | Δ W | the arithmetic mean of instantaneous value of maximum；

The judgment basis of 6.2 sclerotin ceramic glaze surface resistances to chemical corrosion

According to internationally recognized color change difference decision criteria:

The color change difference decision criteria of table 3

Feel the difference degree of color |ΔW| Slightly 0~0.5 It is less 0.5~1.5 Substantially 1.5~3.0 Clearly 3.0~6.0 Significantly 6.0~12.0 It is extremely notable More than 12.0

According to data analysis rule and Common criterion, following classification criterion is taken：

| Δ W |≤0.5 is that color is unchanged, and resistance to chemical corrosion is good；

1.5 >=| Δ W | ＞ 0.5 is color change unobvious, and resistance to chemical corrosion is general；

| Δ W | ＞ 1.5 is that color change is obvious, and resistance to chemical corrosion is poor；

The judgement of 6.3 every groups of Bone China sample glaze paint resistance to chemical corrosion evaluation results

3 samples of every group of difference Bone China sample are derived from after same chemical reagent persistently corrodes specific period, when some Sample whiteness change absolute value | Δ W | maximum be more than this group of sample whiteness change absolute value | Δ W | maximum arithmetic average Value 10% when；Need to extract one group of above-mentioned experimental procedure of sample repetition again；Two groups of Bone China samples are through this examination before and after calculating Each sample whiteness change absolute value after specific period is corroded in agent | Δ W | the arithmetic mean of instantaneous value of maximum, and if some sample is white Degree change absolute value | Δ W | maximum be more than this two groups of 6 sample whiteness change absolute values | Δ W | maximum arithmetic mean of instantaneous value 10%, then abandon it；Take remaining sample whiteness change absolute value | Δ W | the arithmetic mean of instantaneous value of maximum is as the batch Bone China The critical parameter of this resistance to chemical reagent erosion performance of sample, and evaluated according to the 6.2 performance judgments foundations provided.
2. the method for whiteness measure of the change detection sclerotin porcelain glaze paint resistance to chemical corrosion according to claim 1, its It is characterised by, when thermometric is not needed during the heat run, seals the thermometer hole of reaction bulb using rubber stopper.
3. the method for whiteness measure of the change detection sclerotin porcelain glaze paint resistance to chemical corrosion according to claim 1, its It is characterised by, during the heat run during Adjustment Tests solution, as early as possible should pours out original solution in reaction bulb, it is to be tested Dismantled after device cooling and rinsed 1~2 time with running water, then fully rinsed with distilled water.