CN111060498A - Method for testing coating sequence of titanium dioxide film layer - Google Patents
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- CN111060498A CN111060498A CN202010006206.0A CN202010006206A CN111060498A CN 111060498 A CN111060498 A CN 111060498A CN 202010006206 A CN202010006206 A CN 202010006206A CN 111060498 A CN111060498 A CN 111060498A
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention discloses a method for testing the coating sequence of a titanium dioxide film layer, which comprises the following steps: s1, sample pretreatment: removing the organic coating layer on the surface of the titanium dioxide, weighing quantitative titanium dioxide, dissolving the titanium dioxide in an ethanol solution, uniformly mixing, filtering and washing, and drying a filter cake to obtain powder; s2, sample grinding: weighing the powder obtained in the step S1 and grinding the powder; s3, sample premixing: weighing the sample in the step S2, and uniformly mixing the sample with 98% sulfuric acid and hydrofluoric acid solution; s4, acidolysis of a sample: uniformly reacting the liquid obtained in the step S3 at the temperature of 150 ℃ and 180 ℃, diluting and filtering, and carrying out ICP (inductively coupled plasma) test on the content of the coating element in the filtrate; s5, sample analysis: testing the element content of the filtrate at different time, wherein the outer film layer is dissolved firstly, the element content reaches the peak value firstly, the second outer film layer is dissolved subsequently, and the second element content reaches the peak value; the method is simple to operate, low in single-sample testing cost, stable in testing result and good in repeatability, and can accurately analyze the coating sequence of the coating material on the surface of the titanium dioxide.
Description
Technical Field
The invention relates to the technical field of titanium dioxide, in particular to a method for testing the coating sequence of a titanium dioxide film layer.
Background
Titanium dioxide is used as a nontoxic white pigment with stable performance and is widely applied to the fields of plastics, coatings, papermaking, printing ink and the like. The surface of the titanium dioxide which is not coated with the surface has lattice defects, and the titanium dioxide is easy to generate photochemical reaction under the irradiation of ultraviolet rays to degrade matrixes such as paint, plastic and the like, so that the application performances such as weather resistance and the like of the coating are reduced; therefore, the titanium dioxide needs to be subjected to surface treatment and coated with inorganic film layers such as alumina, silica, zirconia, cerium oxide and the like, so that on one hand, the photocatalytic active points on the lattice surface of the titanium dioxide can be shielded, and the weather resistance of the titanium dioxide is improved, and on the other hand, the dispersibility of the titanium dioxide in a coating and other substrates can be improved by coating the inorganic film layers.
Different application performances can be obtained by coating the surface of the titanium dioxide differently, for example, silicon and aluminum coatings are the most classical coatings of the titanium dioxide with high weather resistance, and cerium, aluminum and phosphorus coatings are common in the field of papermaking. The titanium dioxide surface treatment type is complex and variable, different application performances can be embodied by the same amount of coating substances and different coating sequences, and therefore, the analysis of the coating sequence of the film layer becomes more and more important in the field of titanium dioxide development. The method can be used for analyzing the surface components of the substance by combining the nano probe with XPS in the scientific research field, can test the film with the thickness of dozens of nanometers, and has very high cost, and the repeatability and the accuracy of the test result are not high for the uneven film.
Disclosure of Invention
In order to overcome the defects, the invention aims to provide a method for testing the coating sequence of a titanium dioxide film layer, and the invention adopts a special acid-soluble mode combined with ICP test to accurately qualitatively and quantitatively analyze the sequence and the amount of coating substances of the film layer; the method is simple to operate, low in single-sample testing cost, capable of quickly obtaining the coating sequence of the titanium dioxide film layer, stable in testing result, good in repeatability, wide in application range and strong in practicability.
In order to achieve the purpose, the invention is implemented according to the following technical scheme:
a method for testing the coating sequence of a titanium dioxide film layer comprises the following steps:
s1, sample pretreatment: removing the organic coating layer on the surface of the titanium dioxide, and eliminating the interference of organic substances; weighing quantitative titanium dioxide, dissolving the titanium dioxide in an ethanol solution, uniformly mixing the titanium dioxide with a magnetic stirrer, filtering and washing, and drying a filter cake at 105 ℃ to obtain powder;
s2, sample grinding: weighing quantitative powder obtained in the step S1, and grinding the powder by adopting grinding equipment;
s3, sample premixing: weighing a certain amount of the sample obtained in the step S2, mixing the sample with a certain amount of 98% sulfuric acid and hydrofluoric acid solution, and stirring and mixing the mixture uniformly by using a magnetic stirrer;
s4, acidolysis of a sample: keeping the temperature of the uniformly mixed liquid in the step S3 at 150 ℃ and 180 ℃ under the action of heating equipment, and placing the uniformly mixed liquid in a reaction kettle for uniform reaction; sampling at intervals of 10-20min, diluting and filtering, and testing the content of the coating elements in the filtrate by ICP (inductively coupled plasma);
s5, sample analysis: testing the content of elements in the filtrate at different time, drawing a curve of the elements changing along with time, firstly dissolving the outer film layer, firstly reaching the peak value of the element content, then dissolving the second outer film layer, secondly reaching the peak value of the element content, and so on, and judging the coating sequence of the product film layer;
preferably, in step S1, the concentration of the ethanol solution is 75% to 85%, and the magnetic stirring time is 30 to 60 min;
preferably, in step S1, the weight of titanium dioxide is 10-15g, and the amount of ethanol solution is 100-150 mL;
preferably, in the step S2, the weight of the powder in the step S1 is weighed to be 5-10 g;
preferably, in step S2, the pulverizing and grinding device is a three-roll grinder or a universal grinder, and the grinding time is 15-20 min;
preferably, in step S3, the sample in step S2 is weighed to have a mass of 0.2-1.0g, a 98% sulfuric acid dosage of 15-100mL, a hydrofluoric acid dosage of 0.2-10mL, and a magnetic stirring time of 5-15 min;
preferably, in step S4, the heating device is an oven or a heating jacket, the reaction kettle is a polytetrafluoroethylene reaction kettle, and the reaction time is 30-300 min;
preferably, in the step S4, the device used for filtering is a 5-10mL syringe, and the aperture of the filtering membrane of the syringe is 0.25-0.45 [ mu ] m.
Compared with the prior art, the method for testing the coating sequence of the titanium dioxide film layer tests the element content of the solution by acid-dissolving the titanium dioxide under the condition of specific temperature and acidity according to different temperatures, different acidity and different acid-dissolving rates of different film layer sequences; the outer film layer is dissolved firstly, the element content reaches the peak value firstly, the second outer film layer is dissolved subsequently, the element content reaches the peak value secondly, and the like, and the coating sequence of the product film layer is judged.
The method is simple to operate, low in single-sample testing cost, stable in testing result and good in repeatability, and can accurately analyze the coating sequence of the coating material on the surface of the titanium dioxide; the invention has wide application range and strong practicability.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a diagram of the film coating of a test sample according to example 1 of the present invention;
FIG. 2 is a diagram of the film coating of the test sample of example 2;
FIG. 3 is a diagram of the film coating of the test sample of example 3;
FIG. 4 is a diagram of the film coating of the test sample of example 4.
Detailed Description
The invention will be further described with reference to the drawings and specific embodiments, which are illustrative of the invention and are not to be construed as limiting the invention.
Example 1
Weighing 10g of titanium dioxide A, uniformly mixing in 100mL of 75% ethanol solution, dispersing for 30min under magnetic stirring, filtering, washing, removing ethanol, and drying a filter cake at 105 ℃; weighing 5g of the dried sample, and grinding for 15min in a three-roll grinder; weighing 0.2g of ground sample, mixing with 5mL of 98% sulfuric acid and 0.2mL of hydrofluoric acid uniformly, stirring and dispersing for 5min by adopting magnetic force, and then heating in an oven at 150 ℃ for reaction for 120 min; sampling and diluting at intervals of 20min, filtering by using a 5mL syringe and a 0.45 mu m filter membrane, and testing the content of the membrane elements in the filtrate by ICP (inductively coupled plasma); and (4) taking the filtrate at different time to test the content of the element for analysis, drawing a time-varying curve of the element, and analyzing the result.
Example 2
Weighing 15g of titanium dioxide B, uniformly mixing in 120mL of 85% ethanol solution, dispersing for 40min under magnetic stirring, filtering, washing, removing ethanol, and drying a filter cake at 105 ℃; weighing 10g of the dried sample, and grinding for 18min in a three-roll grinder; weighing 0.2g of ground sample, taking 10mL of 98% sulfuric acid and 0.2mL of hydrofluoric acid, magnetically stirring for dispersing for 15min, heating in an oven at 180 ℃, and reacting for 30 min; sampling and diluting every 10min, filtering by using a 5mL syringe and a 0.25 mu m filter membrane, and testing the content of the membrane elements in the filtrate by ICP (inductively coupled plasma); and (4) taking the filtrate at different time to test the content of the element for analysis, drawing a time-varying curve of the element, and analyzing the result.
Example 3
Weighing 12g of titanium dioxide C in 150mL of 80% ethanol solution, uniformly mixing, dispersing for 60min under magnetic stirring, filtering, washing, removing ethanol, and drying a filter cake at 105 ℃; weighing 8g of the dried sample, and grinding for 20min in a three-roll grinder; weighing 0.8g of ground sample, taking 80mL of 98% sulfuric acid and 5mL of hydrofluoric acid, magnetically stirring and dispersing for 10min, then heating in an oven to 165 ℃, and reacting for 180 min; sampling and diluting at intervals of 20min, filtering by using a 10mL injector and a 0.40 mu m filter membrane, and testing the content of the membrane elements in the filtrate by ICP (inductively coupled plasma); and (4) taking the filtrate at different time to test the content of the element for analysis, drawing a time-varying curve of the element, and analyzing the result.
Example 4
Weighing 15g of titanium dioxide D in 150mL of 80% ethanol solution, uniformly mixing, dispersing for 50min under magnetic stirring, filtering, washing, removing ethanol, and drying a filter cake at 105 ℃; weighing 10g of the dried sample, and grinding for 20min in a three-roll grinder; weighing 1.0g of ground sample, taking 100mL of 98% sulfuric acid and 10mL of hydrofluoric acid, magnetically stirring and dispersing for 10min, then heating in an oven to 170 ℃, and reacting for 300 min; sampling and diluting at intervals of 20min, filtering by using a 10mL injector and a 0.35 mu m filter membrane, and testing the content of the membrane elements in the filtrate by ICP (inductively coupled plasma); and (4) taking the filtrate at different time to test the content of the element for analysis, drawing a time-varying curve of the element, and analyzing the result.
Elemental analysis of the sample:
titanium dioxide A, B, C, D is a laboratory coating sample, and titanium dioxide A is a single aluminum coating; titanium dioxide B is a zirconium-aluminum coated film, and zirconium is coated firstly and then aluminum is coated; titanium dioxide C is silicon-aluminum coated, and silicon is coated firstly and then aluminum is coated; titanium dioxide D is a silicon-zirconium-aluminum coated film, silicon is coated firstly, then zirconium is coated, and finally aluminum is coated;
table 1 shows the elemental contents of titanium dioxide A, B, C, D in the examples:
TABLE 1
Example 1 analysis of film coating of test sample:
table 2 is a table of film coating data of the test samples of example 1:
TABLE 2
Fig. 1 is a diagram of the film coating condition of the test sample in example 1, and it can be known from table 2 and fig. 1 that titanium dioxide a is a single aluminum coating, and it can be known from comparison with table 1 that the coating condition is consistent with the inclusion condition of the experiment.
Example 2 analysis of film coating of test sample:
table 3 is a table of film coating data of the test samples of example 2:
TABLE 3
Fig. 2 is a diagram of the coating condition of the test sample film layer in example 2, and it can be known from table 3 and fig. 2 that titanium dioxide B is a zirconium-aluminum coating film, and the coating condition is consistent with the experimental coating condition after zirconium is added.
Table 4 is a table of film coating data of the test samples of example 3:
TABLE 4
Fig. 3 is a diagram of the coating condition of the film layer of the test sample in example 3, and it can be known from table 4 and fig. 3 that the coating condition of the titanium dioxide C silicon-aluminum coating is consistent with the experimental coating condition after silicon is firstly coated and then aluminum is coated.
Example 4 analysis of film coating of test sample:
table 5 is a table of film coating data for the test samples of example 4:
TABLE 5
Fig. 4 is a diagram of the coating condition of the test sample film layer in example 4, and it can be known from table 5 and fig. 4 that titanium dioxide D is a silicon-zirconium-aluminum coating film, and silicon is first followed by zirconium, and finally aluminum is consistent with the experimental coating condition.
The technical solution of the present invention is not limited to the limitations of the above specific embodiments, and all technical modifications made according to the technical solution of the present invention fall within the protection scope of the present invention.
Claims (8)
1. A method for testing the coating sequence of a titanium dioxide film layer is characterized by comprising the following steps:
s1, sample pretreatment: removing the organic coating layer on the surface of the titanium dioxide, and eliminating the interference of organic substances; weighing quantitative titanium dioxide, dissolving the titanium dioxide in an ethanol solution, uniformly mixing the titanium dioxide with a magnetic stirrer, filtering and washing, and drying a filter cake at 105 ℃ to obtain powder;
s2, sample grinding: weighing quantitative powder obtained in the step S1, and grinding the powder by adopting grinding equipment;
s3, sample premixing: weighing a certain amount of the sample obtained in the step S2, and uniformly mixing the sample with a certain amount of 98% sulfuric acid and hydrofluoric acid solution by using a magnetic stirrer;
s4, acidolysis of a sample: keeping the temperature of the uniformly mixed liquid in the step S3 at 150 ℃ and 180 ℃ under the action of heating equipment, and placing the uniformly mixed liquid in a reaction kettle for uniform reaction; sampling at intervals of 10-20min, diluting and filtering, and testing the content of the coating elements in the filtrate by ICP (inductively coupled plasma);
s5, sample analysis: and testing the content of the elements in the filtrate at different time, drawing a curve of the elements changing along with time, firstly dissolving the outer film layer, firstly reaching the peak value of the content of the elements, then dissolving the second outer film layer, secondly reaching the peak value of the content of the elements, and so on, and judging the coating sequence of the product film layers.
2. The method for testing the coating sequence of the titanium dioxide film layer according to claim 1, wherein in step S1, the concentration of the ethanol solution is 75-85%, and the magnetic stirring time is 30-60 min.
3. The method for testing the coating sequence of the titanium dioxide film layer as claimed in claim 2, wherein in step S1, the mass of the titanium dioxide is 10-15g, and the amount of the ethanol solution is 100-150 mL.
4. The method for testing the coating sequence of the titanium dioxide film layer according to claim 1, wherein in the step S2, the weight of the powder in the step S1 is weighed to be 5-10 g.
5. The method for testing the coating sequence of titanium dioxide film according to claim 4, wherein in step S2, the grinding and milling equipment is a three-roll mill or a universal mill, and the grinding time is 15-20 min.
6. The method for testing the coating sequence of the titanium dioxide film layer according to claim 1, wherein in step S3, the sample in step S2 is weighed to have a mass of 0.2-1.0g, the amount of 98% sulfuric acid is 15-100mL, the amount of hydrofluoric acid is 0.2-10mL, and the magnetic stirring time is 5-15 min.
7. The method for testing the coating sequence of the titanium dioxide film layer according to claim 1, wherein in step S4, the heating equipment is an oven or a heating jacket, the reaction kettle is a polytetrafluoroethylene reaction kettle, and the reaction time is 30-300 min.
8. The method for testing the coating sequence of the titanium dioxide film layer according to claim 7, wherein in the step S4, the equipment used for filtering is a 5-10mL injector, and the aperture of the filtering film of the injector is 0.25-0.45 μm.
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Citations (5)
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| JP2003045927A (en) * | 2001-07-26 | 2003-02-14 | Mitsui Chemical Analysis & Consulting Service Inc | Method for analyzing multilayer film on substrate surface for each layer |
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| JP2012154750A (en) * | 2011-01-25 | 2012-08-16 | Fujitsu Ltd | Method for analyzing element concentration in depth direction |
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| CN109916930A (en) * | 2019-03-27 | 2019-06-21 | 龙蟒佰利联集团股份有限公司 | A method of test titanium dioxide internal layer silicon fiml pattern |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003045927A (en) * | 2001-07-26 | 2003-02-14 | Mitsui Chemical Analysis & Consulting Service Inc | Method for analyzing multilayer film on substrate surface for each layer |
| JP2007198797A (en) * | 2006-01-24 | 2007-08-09 | Hitachi High-Technologies Corp | Quantitative analyzer and analyzing method |
| JP2012154750A (en) * | 2011-01-25 | 2012-08-16 | Fujitsu Ltd | Method for analyzing element concentration in depth direction |
| CN108801953A (en) * | 2018-06-28 | 2018-11-13 | 四川龙蟒钛业股份有限公司 | The assay method of titanium coating content in a kind of titanium dioxide |
| CN109916930A (en) * | 2019-03-27 | 2019-06-21 | 龙蟒佰利联集团股份有限公司 | A method of test titanium dioxide internal layer silicon fiml pattern |
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