CN103439167B - A kind of preparation method of leaded ceramic glaze standard sample - Google Patents
A kind of preparation method of leaded ceramic glaze standard sample Download PDFInfo
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- CN103439167B CN103439167B CN201310413783.1A CN201310413783A CN103439167B CN 103439167 B CN103439167 B CN 103439167B CN 201310413783 A CN201310413783 A CN 201310413783A CN 103439167 B CN103439167 B CN 103439167B
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Abstract
The present invention relates to a kind of preparation method of leaded ceramic glaze standard sample, the method is through batch mixing, grinding, granulation, shaping and burn till step and obtain leaded ceramic glaze standard sample.Leaded ceramic glaze standard sample prepared by the inventive method has lead content definite value accurately, and Determination of Pb result fluctuation range is less, and quantitative test plumbous in ceramic glaze layer can be made more accurate; Preparation process is simple, and operating environment is friendly, is easy to apply; The invention solves puzzlement ceramic industry for many years cannot to lead content accurate quantitative analysis in ceramic glaze layer, and ceramic glaze to be measured is without the problem of standard model or standard model deficiency, the science for the lead content in ceramic glaze detects to analyze and has supplied strong technological means.
Description
Technical field
The present invention relates to a kind of preparation method of leaded ceramic glaze standard sample, belong to the technical field of metered amount value transmit.
Background technology
In order to make porcelain not seep water and attractive in appearance, often need for its glazing and painted.Lead glaze is excellent with its meltbility, good luster, elasticity are large and firing range is wide etc., and advantage is widely used, but the lead in lead glaze is poisonous, the healthy of people is harmful to, can affect the nerves, hematopoiesis, each organoid such as digestion, more seriously it affects growth and the intelligent development of infant, severe patient causes dementia, and the improvement infringement that lead causes is irreversible.Therefore, in crockery, the detection of lead content is very important, and content of heavy metal lead in ceramic outer decorative cover is limited the outlet of China's ceramic by the developed countries such as the U.S., Canada, European Union as new skill error, and has increasingly strict gesture.
At present, chemical analysis, x ray fluorescence spectrometry (XRF) etc. is had in the method that ceramic glaze detection field is conventional; Chemical analysis accuracy in detection is the highest, and testing result value is close to true value, but very very complicated, detection speed are slow for chemical analysis detecting step, and needs to destroy ceramic, and application limitation is very large; Owing to having, with high accuracy, speed is fast, the concentration range of analytical element is wide, sample pre-treatments simple and the advantage such as Non-Destructive Testing can be applied to ceramic research field for x ray fluorescence spectrometry (XRF).Develop a series ofly have that chemistry similar forms with domestic ceramics glaze, thing phase composition, density the leaded ceramic glaze standard sample standard specimen that performs an analysis, the factors such as the precision of matrix effect, physical parameter in XRF analysis test process, stability of instrument that can solve are on the impact of result precision.But the preparation due to ceramic glaze standard sample faces preparation technology's difficult problems such as calcining system control, formula Design, want to prepare the ceramic glaze labor standard sample meeting the requirement of standard model definite value and there is very large technical difficulty.At present, the preparation method for analyzing the leaded ceramic glaze standard sample detecting ceramic glaze layer lead content has no report.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of leaded ceramic glaze standard sample.
Summary of the invention
Whether standard substance has definite value is accurately the important indicator of research standard material, is the prerequisite that reference material mass-energy gains public acceptance, and is the basis of metered amount value transmit.Due to many-sided reason such as long-time stability of the uncertainty in the unevenness of sample to be tested, analysis to measure process, material, all may cause and analyze the inconsistent of data; The present invention gives the concept of uncertainty, object is, when analyze data within the data variation scope of given standard definite value and uncertainty time, then think that it is reliable for analyzing data, otherwise then think that analysis data are unreliable.Primary study of the present invention formula and firing temperature technique, on the impact of standard model definite value, are prepared and are had accurate lead content definite value and the leaded ceramic glaze standard sample meeting standard substance requirement, make the detection of ceramic glaze lead content more accurate.
Term explanation
Containing dithizone: of the present inventionly refer to solid chemicals containing lead element containing dithizone, comprise plumbous compound etc.
Blank ceramic glaze: blank ceramic glaze of the present invention refers to lead-free fritting enamel.
Uncertainty: uncertainty of the present invention refers to the value fluctuation range residing for measured true value.
Technical scheme of the present invention is as follows:
A preparation method for leaded ceramic glaze standard sample, step is as follows:
(1) batch mixing: will be 1:(3 ~ 6000 in mass ratio containing dithizone, blank ceramic glaze and cementing agent): (0.8 ~ 1500) mixes, and obtains mixture;
(2) grind: mixture and water press 1:(8 ~ 12) mass ratio mix, add abrading-ball and be milled to grain diameter≤74 μm, be placed in drying box 100 ~ 110 DEG C of drying 6 ~ 10h, obtain dry powder;
(3) granulation: spray the moisture of 3 ~ 5% dry powder qualities and be evenly distributed in the dry powder after oven dry, obtaining compressing tablet raw material;
(4) shaping: by compressing tablet raw material on sheeter in the tableting under pressure of 18 ~ 22MPa, put into baking oven and dry, obtain compressing tablet sample;
(5) burn till: compressing tablet sample is placed in muffle furnace, with the speed of 3 ~ 5 DEG C/min insulation 1 ~ 2h behind room temperature to 670 ~ 750 DEG C, naturally cool to room temperature, obtain leaded ceramic glaze standard sample.
According to the present invention, preferably, the one be selected from containing dithizone in lead orthoplumbate, plumbi nitras, lead chloride described in step (1); Described blank ceramic glaze is selected from the one in Lead-free transparent fritted glaze or Lead-free opalescent frit glaze;
Preferred, the chemical composition of described Lead-free transparent fritted glaze is: 0.5 ~ 2.0%Na
2o, 1.0 ~ 2.5%MgO, 7.0 ~ 10.0%Al
2o
3, 60 ~ 72.0%SiO
2, 2.0 ~ 3.0%K
2o, 8.0 ~ 16.0%CaO, 5.0 ~ 8.0%Fe
2o
3, 0.1 ~ 0.5%ZrO
2, 0.3 ~ 1.0%BaO, 1.5 ~ 5.0%ZnO, 0.1 ~ 1.0%SO
3;
The chemical composition of described Lead-free opalescent frit glaze is: 0.1 ~ 2.0%Na
2o, 0.5 ~ 3.0%MgO, 4.0 ~ 10.0%Al
2o
3, 55.0 ~ 80.0%SiO
2, 1.0 ~ 4.0%K
2o, 6.0 ~ 17.0%CaO, 2.0 ~ 7.0%Fe
2o
3, 0.1 ~ 1.0%ZrO
2, 0.2 ~ 1.0%BaO, 2.0 ~ 6.0%ZnO, 0.1 ~ 1.0%SO
3;
Described cementing agent is selected from the one in carboxymethyl cellulose, paraffin, methylcellulose or microcrystalline cellulose.
According to the present invention, preferably, the mass ratio of the mixture described in step (2) and abrading-ball is 1:(15 ~ 20);
Preferred, the mass ratio of mixture, abrading-ball and the water described in step (2) is 1:18:10.
According to the present invention, preferably, the temperature of drying in the baking oven described in step (4) is 105 ~ 120 DEG C, and drying time is 5 ~ 12h, and described compressing tablet sample is the disk sample of diameter 32mm, thick 2 ~ 4mm.
According to the present invention, preferably, in step (5) with the speed of 4 DEG C/min from room temperature to 680 ~ 730 DEG C.
Raw materials usedly in the present invention be commercial products.
Leaded ceramic glaze standard sample of the present invention not only can be applied to x ray fluorescence spectrometry (XRF), can also be applied to other analytical approachs such as micro-wave digestion-ICP method, laser ablation-ICP-MS method etc. and carry out qualitative and quantitative analysis to the leaded situation in ceramic and glaze layer.
The leaded ceramic glaze standard sample utilizing the inventive method to prepare carries out qualitative and quantitative analysis by prior art to the leaded situation in ceramic glaze layer.
Beneficial effect of the present invention is as follows;
1, the leaded ceramic glaze standard sample that prepared by the inventive method has lead content definite value accurately, and Determination of Pb result fluctuation range is less, and the leaded situation quantitative test in ceramic glaze layer can be made more accurate.
2, the preparation process of the leaded ceramic glaze standard sample of the present invention is simple, and operating environment is friendly, is easy to apply.
3, the invention solves puzzlement ceramic industry for many years cannot to ceramic glaze layer lead content accurate quantitative analysis, and ceramic to be measured is without the problem of standard model or standard model deficiency, the science for the lead tolerance in ceramic glaze layer detects to analyze and has supplied strong technological means.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph (SEM) of leaded ceramic glaze standard sample prepared by the embodiment of the present invention 1.
Fig. 2 is the photo in kind of leaded ceramic glaze standard sample prepared by the embodiment of the present invention 1.
Fig. 3 is massicot x ray fluorescence spectrometry (XRF) the analytical standard working curve of leaded ceramic glaze standard sample foundation prepared by embodiment of the present invention 1-7.
Embodiment
Below by specific embodiment, the present invention will be further described, but be not limited thereto.
Lead tolerance described in embodiment, comparative example and application examples is the mass percentage of lead element.
Raw materials usedly in embodiment be convenient source, commercial products, analyze pure; Device therefor is conventional commercial equipment.
Wherein: Lead-free transparent fritted glaze, Lead-free opalescent frit glaze, great Hong enamel frit makeing company limited is on sale.
The equipment of x ray fluorescence spectrometry analysis is the Axios SuperQ of Dutch PANalytical, U.S.'s match is silent flies your ARL, German Brooker S8TIGER of generation.
Embodiment 1,
The preparation that lead tolerance is 0.016%, uncertainty is the leaded ceramic glaze standard sample of ± 0.001%, step is as follows:
(1) batch mixing: take lead orthoplumbate 0.004g in 24.00g Lead-free transparent fritted glaze, adds 6.00g microcrystalline cellulose and mixes, obtain mixture;
(2) grind: mixture, abrading-ball and water mixed by the mass ratio of 1:15:8 and is milled to grain diameter≤74 μm, being placed in drying box 105 DEG C of dry 8h, obtaining dry powder;
(3) granulation: spray the moisture of 4% dry powder quality and be evenly distributed in the dry powder after oven dry, obtaining compressing tablet raw material;
(4) shaping: get 10.0g compressing tablet raw material makes diameter 32mm, thick 3mm on sheeter disc sample in the pressure of 20MPa, in baking oven, 120 DEG C of dry 8h, obtain compressing tablet sample;
(5) burn till: compressing tablet sample is placed in muffle furnace, after room temperature to 750 DEG C, be incubated 1.5h with the speed of 4 DEG C/min, naturally cool to room temperature, obtain leaded ceramic glaze standard sample.
In the present embodiment, the chemical composition of Lead-free transparent fritted glaze is: Na
2o (0.72%), MgO (1.17%), Al
2o
3(8.08%), SiO
2(66.38%), K
2o (2.41%), CaO (11.88%), Fe
2o
3(5.05%), ZrO
2(0.19%), BaO (0.41%), ZnO (3.52%), SO
3(0.19%).
Fig. 1 is the SEM photo of leaded ceramic glaze standard sample prepared by the present embodiment, and as can be seen from Figure 1 leaded ceramic glaze standard sample compact structure, exists without obvious crystal grain, and amount of glassy phase is very high, and vitrifacation degree is high.
Fig. 2 be the leaded ceramic glaze standard sample prepared of the present embodiment photo in kind, as can be seen from Figure 2 leaded ceramic glaze standard sample structure is very fine and close, defines the distinctive micromechanism of ceramic glaze layer.
The definite value of leaded ceramic glaze standard sample and the determination of uncertainty: according to GB/T15000.3-2008 " rule of standard model work directive/guide (3) standard model definite value and statistical method " and CNAS-GL29:2010 " rule of standard substance-standard model definite value and statistical method " requirement, participate in the number of the cooperation experiment room of analysis definite value, be generally no less than 6 laboratories.Participate in the analysis data group number of definite value and be generally no less than 8 groups, each laboratory often four independent test data quoting of the method for planting as one group of data.The present embodiment takes Duo Jia laboratory, multiple analysis means carries out cooperation definite value to standard model, and guarantee the accuracy of mean value, analytical approach all adopts national standard or industry standard.Adopt variance method, Cochran, summer Pyrrho method, Rod Dixon method to each group of value data carry out uniformity testing, equally accurate inspection, normality distribution inspection and stability test qualified after, last definite value; Concrete steps are as follows:
(1) sample: each gradient extracts print by random number, send to domestic 10 to have the unit cooperation definite value that better standard specimen definite value analyzes experience.
(2) definite value analytical approach: according to national standard sample technical manual, definite value unit selects one or both definite values of analytical approach cooperation accurately and reliably, analyzes main to adopt national standard method GB/T14506-2010 " silicate rock chemical analysis method ", GB/T4734-1996 " stupalith and goods chemical analysis method ", GB/T1347-2008 " soda-lime-silica glass chemical analysis method " and industry standard the mensuration plasma emlssion spectrometry of primary and secondary quantitative elements " in the domestic glass product ".
(3) uniformity testing: according to variance method check sample homogeneity.The uniformity testing result F value of each element is all less than critical value (getting level of significance a=0.05), and standard model is judged to be evenly, can carry out data processing below.
(4) outlier inspection: between the interior data outlier of result group quoted constituent parts with Rod Dixon test criterion and group, data outlier is checked and accepts or rejects, can carry out data processing below after outlier between rejecting group interior and group.
(5) equally accurate inspection: carry out equally accurate inspection to the result that constituent parts is quoted by Cochran-test criterion, carries out data processing below after deleting suspicious data group.
(6) test of normality: the test of normality of determination data adopts gram inspection of Xia Piluo-Weir, and look into specific normality W and check tables of critical values, data, all in normal distribution, can carry out data processing below.
(7) stability test: in 22 months, this standard model has carried out four times stage by stage and has measured, and the measured value of each element does not produce significantly is inclined to trend, and having good stability of this standard model is described.Situation is preserved in the use of using for reference national and foreign standards sample, and under the preservation condition of regulation, the term of validity of this standard sample is about 2 years.
(8) expression of definite value result: select definite value principle and statistical method according to GB/T15000.3-2008 standard model work directive/guide (3) standard model, by the mean value of each laboratory, each test mode test data, be considered as single test value, definite value result is by population mean
represent with the standard deviation S of single test value, provide the test data set number participating in definite value simultaneously.
In formula
constituent parts testing mean;
M-test data set number;
Uncertainty embodies with standard deviation and test data set number.Carry out the numerical value revision of the convention by GB8170, standard value figure place is alignd with standard deviation figure place, and standard deviation does not give up process by only entering.
Lead content in x-ray fluorescence spectrometry sample ceramic glaze layer:
The leaded ceramic glaze standard sample prepared by the present embodiment is put into Xray fluorescence spectrometer and is set up calibration operation curve, utilizes the tlc analysis software in Xray fluorescence spectrometer to carry out analysis to sample and measures.Wherein the density value of the hierarchy number of measuring samples, the thickness of sample and sample (is generally 1g/cm
3) input in analysis software, content plumbous in testing sample glaze layer can be measured according to the iteration theorem of intensity.
Embodiment 2,
The preparation that lead tolerance is 0.097%, uncertainty is the leaded ceramic glaze standard sample of ± 0.001%, step is with example 1, and difference is:
0.05g plumbi nitras is added as containing dithizone in step (1);
In step (5), temperature retention time is 1.5h.
In the present embodiment, the chemical composition of Lead-free transparent fritted glaze is: Na
2o (0.69%), MgO (1.12%), Al
2o
3(7.88%), SiO
2(68.63%), K
2o (2.16%), CaO (10.89%), Fe
2o
3(4.43%), ZrO
2(0.19%), BaO (0.38%), ZnO (3.43%), SO
3(0.20%).
Embodiment 3,
The preparation that lead tolerance is 1.93%, uncertainty is the leaded ceramic glaze layer standard model of ± 0.01%, step is as follows:
(1) batch mixing: take lead orthoplumbate 0.54g in 23.50g Lead-free opalescent frit glaze, adds 5.50g microcrystalline cellulose and mixes, obtain mixture;
(2) grind: mixture, abrading-ball and water mixed by the mass ratio of 1:20:8 and is milled to grain diameter≤74 μm, being placed in drying box 105 DEG C of dry 8h, obtaining dry powder;
(3) granulation: spray the moisture of 4% dry powder quality and be evenly distributed in the dry powder after oven dry, obtaining compressing tablet raw material;
(4) shaping: get 10.00g compressing tablet raw material makes diameter 32mm, thick 3mm on sheeter disc sample in the pressure of 20MPa, in baking oven, 120 DEG C of dry 8h, obtain compressing tablet sample;
(5) burn till: compressing tablet sample is placed in muffle furnace, after room temperature to 730 DEG C, be incubated 1h with the speed of 5 DEG C/min, naturally cool to room temperature, obtain leaded ceramic glaze standard sample.
In the present embodiment, the chemical composition of Lead-free opalescent frit glaze is: Na
2o (1.75%), MgO (1.32%), Al
2o
3(8.58%), SiO
2(62.28%), K
2o (2.58%), CaO (12.68%), Fe
2o
3(5.45%), ZrO
2(0.16%), BaO (0.45%), ZnO (3.78%), SO
3(0.97%).
Embodiment 4,
The preparation that lead tolerance is 8.30%, uncertainty is the leaded ceramic glaze layer standard model of ± 0.03%, step is with example 1, and difference is:
Take 3.10g lead chloride in step (1) in 21.00g Lead-free opalescent frit glaze, add 5.10g microcrystalline cellulose and mix, obtain mixture;
1h is incubated after being warming up to 720 DEG C in step (5).
In the present embodiment, the chemical composition of Lead-free opalescent frit glaze is: Na
2o (0.44%), MgO (0.76%), Al
2o
3(5.29%), SiO
2(78.27%), K
2o (1.56%), CaO (7.61%), Fe
2o
3(2.99%), ZrO
2(0.14%), BaO (0.29%), ZnO (2.09%), SO
3(0.56%).
Embodiment 5,
The preparation that lead tolerance is 12.47%, uncertainty is the leaded ceramic glaze layer standard model of ± 0.04%, step is with example 1, and difference is:
Take 3.50g lead orthoplumbate in step (1) in 20.50g Lead-free transparent fritted glaze, add 5.10g microcrystalline cellulose and mix, obtain mixture;
1h is incubated after being warming up to 710 DEG C in step (5).
In the present embodiment, the chemical composition of Lead-free transparent fritted glaze is: Na
2o (0.80%), MgO (1.36%), Al
2o
3(9.08%), SiO
2(63.09%), K
2o (2.62%), CaO (13.06%), Fe
2o
3(5.32%), ZrO
2(0.23%), BaO (0.49%), ZnO (3.79%), SO
3(0.16%).
Embodiment 6,
The preparation that lead tolerance is 20.43%, uncertainty is the leaded ceramic glaze layer standard model of ± 0.01%, step is as follows:
(1) batch mixing: take lead orthoplumbate 5.20g in 18.80g Lead-free transparent fritted glaze, adds 4.60g microcrystalline cellulose and mixes, obtain mixture;
(2) grind: mixture, abrading-ball and water mixed by the mass ratio of 1:15:12 and is milled to grain diameter≤74 μm, being placed in drying box 105 DEG C of dry 8h, obtaining dry powder;
(3) granulation: spray the moisture of 4% dry powder quality and be evenly distributed in the dry powder after oven dry, obtaining compressing tablet raw material;
(4) shaping: get 10g compressing tablet raw material makes diameter 32mm, thick 3mm on sheeter disc sample in the pressure of 20MPa, in baking oven, 120 DEG C of dry 8h, obtain compressing tablet sample;
(5) burn till: compressing tablet sample is placed in muffle furnace, after room temperature to 670 DEG C, be incubated 1h with the speed of 3 DEG C/min, naturally cool to room temperature, obtain leaded ceramic glaze standard sample.
In the present embodiment, the chemical composition of Lead-free transparent fritted glaze is with embodiment 1.
Embodiment 7,
The preparation that lead tolerance is 18.57%, uncertainty is the leaded ceramic glaze layer standard model of ± 0.03%, step is with example 1, and difference is:
The lead orthoplumbate quality of adding in step (1) is 5.32g;
1h is incubated after being warming up to 680 DEG C in step (5).
In the present embodiment, the chemical composition of Lead-free transparent fritted glaze is with embodiment 1.
Comparative example,
This comparative example fusion method preparation standard sample, step is as follows:
(1) batch mixing: take and analyze pure lead orthoplumbate 0.0035g in 0.6965g Lead-free transparent frit glaze, the mixed solvent (lithium tetraborate: lithium metaborate=63:27, mass ratio) adding 7g lithium tetraborate and lithium metaborate is in platinum crucible and mix;
(2) melting: add 4 ~ 5 release agents in the powder of mixing, crucible is put into high temperature smelting furnace in 1050 DEG C of meltings, pour fused solution into shaping grinding apparatus, after cooling, the demoulding obtains flint glass melting standard model sheet;
The pure lead orthoplumbate of analysis and the Lead-free transparent frit glaze (gross mass of lead orthoplumbate and Lead-free transparent frit glaze is 0.7g) of different quality ratio is taken respectively, the glass melting standard model sheet of obtained a series of different lead tolerance according to the step in comparative example.
In this comparative example, the chemical composition of Lead-free transparent fritted glaze is with embodiment 1.
Application examples,
Market should be buied 9 groups of leaded ceramics as testing sample by use-case, utilize chemical analysis to measure lead tolerance in 9 groups of ceramics sample glaze layers to be measured as quantitative values.
The leaded ceramic glaze standard sample utilizing embodiment and comparative example to prepare, as standard model, measures lead tolerance in ceramics sample glaze layer to be measured by X-ray fluorescence spectra.
Leaded ceramic glaze standard sample embodiment prepared is put into Xray fluorescence spectrometer and is detected and set up calibration operation curve, and employing standard working curve method measures the lead tolerance in ceramics sample glaze layer to be measured, and testing result is in table 1.
A series of flint glass melting standard model sheets comparative example prepared are put into Xray fluorescence spectrometer and are detected and set up calibration operation curve, and employing standard working curve method measures the lead tolerance in ceramics sample glaze layer to be measured, and testing result is in table 2.
Table 1
| Testing sample | The lead content of the testing sample that embodiment obtains | Chemical analysis quantitative values | Relative deviation |
| 1# | 8.277% | 8.289% | -0.14% |
| 2# | 12.466% | 12.464% | 0.02% |
| 3# | 20.464% | 20.423% | 0.20% |
| 4# | 0.346% | 0.345% | 0.29% |
| 5# | 0.836% | 0.840% | -0.48% |
| 6# | 2.141% | 2.148% | -0.33% |
| 7# | 0.083% | 0.080% | 3.75% |
| 8# | 0.807% | 0.813% | -0.74% |
| 9# | 1.970% | 1.963% | 0.36% |
Table 2
| Testing sample | The lead content of the testing sample that comparative example obtains | Chemical analysis quantitative values | Relative deviation |
| 1# | 6.648% | 8.289% | -19.80% |
| 2# | 9.185% | 12.464% | -26.31% |
| 3# | 15.496% | 20.423% | -24.12% |
| 4# | 0.262% | 0.345% | -24.06% |
| 5# | 0.541% | 0.840% | -35.60% |
| 6# | 1.824% | 2.148% | -15.08% |
| 7# | 0.057% | 0.080% | -28.75% |
| 8# | 0.563% | 0.813% | -30.75% |
| 9# | 1.276% | 1.963% | -35.00% |
As can be seen from table 1, table 2, the lead tolerance in the ceramics sample glaze layer to be measured that the leaded ceramic glaze standard sample prepared of embodiment detects as standard model and the relative deviation of chemical analysis quantitative values very little, testing result accuracy is high; And the relative deviation of lead content in the ceramics sample glaze layer to be measured that detects as standard model of flint glass melting standard model sheet prepared by comparative example and chemical analysis quantitative values is very large, testing result poor accuracy, is not suitable as the quantitative analysis method of unknown ceramics sample glaze layer.
Claims (1)
1. a preparation method for leaded ceramic glaze standard sample, step is as follows:
(1) batch mixing: will be 1:(3 ~ 6000 in mass ratio containing dithizone, blank ceramic glaze and cementing agent): (0.8 ~ 1500) mixes, and obtains mixture;
Described blank ceramic glaze is selected from the one in Lead-free transparent fritted glaze or Lead-free opalescent frit glaze;
(2) grind: mixture and water press 1:(8 ~ l2) mass ratio mix, add abrading-ball and be milled to grain diameter≤74 μm, be placed in drying box 100 ~ 110 DEG C of drying 6 ~ 10h, obtain dry powder;
(3) granulation: spray the moisture of 3 ~ 5% dry powder qualities and be evenly distributed in the dry powder after oven dry, obtaining compressing tablet raw material;
(4) shaping: by compressing tablet raw material on sheeter in the tableting under pressure of 18 ~ 22 MPa, put into baking oven and dry, obtain compressing tablet sample;
(5) burn till: compressing tablet sample is placed in muffle furnace, behind room temperature to 670 ~ 750 DEG C, be incubated l ~ 2h with the speed of 3 ~ 5 DEG C/min, naturally cool to room temperature, obtain leaded ceramic glaze standard sample.
2
.the preparation method of leaded ceramic glaze standard sample according to claim 1, is characterized in that, the one be selected from containing dithizone in lead orthoplumbate, plumbi nitras, lead chloride described in step (1).
3
.the preparation method of leaded ceramic glaze standard sample according to claim 1, is characterized in that, the chemical composition of the Lead-free transparent fritted glaze described in step (1) is: 0.5 ~ 2.0% Na
2o, 1.0 ~ 2.5% MgO, 7.0 ~ 10.0% Al
2o
3, 60 ~ 72.0% SiO
2, 2.0 ~ 3.0% K
2o, 8 ~ 16.0% CaO, 5.0 ~ 8.0% Fe
2o
3, 0.1 ~ 0.5% ZrO
2, 0.3 ~ 1.0% BaO, 1.5 ~ 5.0% ZnO, 0.1 ~ 1.0% SO
3.
4
.the preparation method of leaded ceramic glaze standard sample according to claim 1, is characterized in that, the chemical composition of the Lead-free opalescent frit glaze described in step (1) is: 0.1 ~ 2.0% Na
2o, 0.5 ~ 3.0% MgO, 4.0 ~ 10.0% Al
2o
3, 55.0 ~ 80.0% SiO
2, 1.0 ~ 4.0% K
2o, 6.0 ~ 17.0% CaO, 2.0 ~ 7.0% Fe
2o
3, 0.1 ~ 1.0% ZrO
2, 0.2 ~ 1.0% BaO, 2.0 ~ 6.0% ZnO, 0.1 ~ 1.0% SO
3.
5
.the preparation method of leaded ceramic glaze standard sample according to claim 1, is characterized in that, the cementing agent described in step (1) is selected from the one in carboxymethyl cellulose, paraffin, methylcellulose or microcrystalline cellulose.
6
.the preparation method of leaded ceramic glaze standard sample according to claim 1, is characterized in that, the mass ratio of the mixture described in step (2) and abrading-ball is 1:(15 ~ 20).
7
.the preparation method of leaded ceramic glaze standard sample according to claim 6, is characterized in that, the mass ratio of mixture, abrading-ball and the water described in step (2) is 1:18:10.
8
.the preparation method of leaded ceramic glaze standard sample according to claim 1, is characterized in that, the temperature of drying in the baking oven described in step (4) is 105 ~ 120 DEG C, and drying time is 5 ~ 12h.
9
.the preparation method of leaded ceramic glaze standard sample according to claim 1, is characterized in that, in step (5) with the speed of 4 DEG C/min from room temperature to 680 ~ 730 DEG C.
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| JPS5931439A (en) * | 1982-08-16 | 1984-02-20 | Kawasaki Steel Corp | Preparation of standard sample of glass bead for optical x-ray analysis |
| CN1298844A (en) * | 1999-12-03 | 2001-06-13 | 淄博工业陶瓷厂 | Lead-free fritting enamel for high-grade porcelain |
| JP2003194683A (en) * | 2001-12-28 | 2003-07-09 | Japan Organo Co Ltd | Preparation method of analytical sample and quantitative analysis method of element |
| CN102539207A (en) * | 2011-12-27 | 2012-07-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing standard sample for testing content of hard-alloy components and method for testing content of hard-alloy components |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5931439A (en) * | 1982-08-16 | 1984-02-20 | Kawasaki Steel Corp | Preparation of standard sample of glass bead for optical x-ray analysis |
| CN1298844A (en) * | 1999-12-03 | 2001-06-13 | 淄博工业陶瓷厂 | Lead-free fritting enamel for high-grade porcelain |
| JP2003194683A (en) * | 2001-12-28 | 2003-07-09 | Japan Organo Co Ltd | Preparation method of analytical sample and quantitative analysis method of element |
| CN102539207A (en) * | 2011-12-27 | 2012-07-04 | 攀钢集团攀枝花钢铁研究院有限公司 | Method for preparing standard sample for testing content of hard-alloy components and method for testing content of hard-alloy components |
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| 高掺量煤渣制备陶瓷釉面砖的研究;程小苏 等;《中国陶瓷》;20110331;第47卷(第3期);第1.1-1.4节，图1、表2-3 * |
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