CN114894828A - Method for rapidly detecting contents of titanium and zirconium in aluminum alloy passivation film - Google Patents
Method for rapidly detecting contents of titanium and zirconium in aluminum alloy passivation film Download PDFInfo
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Abstract
The invention discloses a method for rapidly detecting the contents of titanium and zirconium in an aluminum alloy passivation film, which relates to the technical field of detection and analysis, is realized by using a wavelength dispersion type X-ray fluorescence spectrometer, and comprises the following steps: establishing a standard sample database, establishing a detection method, setting detection parameters, calibrating the detection method, verifying accuracy, detecting a sample and calculating a result. The method is realized by using the wavelength dispersion type X-ray fluorescence spectrometer by establishing the quantitative detection method of the titanium and zirconium contents in the aluminum alloy passivation film on the wavelength dispersion type X-ray fluorescence spectrometer by utilizing the characteristic of high power of the wavelength dispersion type X-ray, and the method has the advantages of large detection area, more representative sample, low lower detection limit of the sample, high sensitivity, good accuracy and repeatability, quick detection and high detection efficiency.
Description
Technical Field
The invention relates to the technical field of detection and analysis, in particular to a method for rapidly detecting contents of titanium and zirconium in an aluminum alloy passivation film.
Background
The aluminum alloy has small density, high specific strength and good comprehensive performance, and is widely applied to the aspect of automobile light weight. An oxide film formed by the aluminum alloy in a natural environment has poor corrosion resistance, so that after the aluminum alloy is subjected to heat treatment, passivation treatment is required to be carried out on the surface of the aluminum alloy so as to effectively protect the surface of the aluminum alloy. The titanium zirconium passive film has good corrosion resistance, can effectively protect the surface of the aluminum material, does not influence the conductivity of the aluminum alloy, has no adverse effect on downstream processes such as electrophoretic coating and the like, is relatively environment-friendly, and gradually replaces a chromate passive film which has harm to human bodies and the environment.
The passivation effect is expressed by the amount of change of the contents of titanium and zirconium in the passivation film before and after passivation, and the unit of the change is mg/m 2 . In order to meet the use requirements of customers, the contents of titanium and zirconium in the aluminum alloy passivation film need to be controlled within a certain range, so that a method capable of accurately measuring the contents of titanium and zirconium in the aluminum alloy passivation film is needed.
The existing detection method mainly adopts an energy dispersion X-ray fluorescence detection technology, uses a titanium and/or zirconium-containing standard sample to calibrate an X-ray fluorescence spectrometer, draws a calibration working curve, respectively detects a blank sample and a sample to be detected, and subtracts the result of the blank sample from the result of the sample to be detected to obtain the content of titanium and/or zirconium in a passive film.
For example, CN110243810A discloses a method for testing the zirconium content in a conversion film on the surface of a metal material, and the article "determination of zirconium and titanium content in 6016 aluminum alloy passivation film by X-ray fluorescence spectrometry" previously published by the applicant all adopt an energy dispersive X-ray fluorescence detection technology to detect the titanium or zirconium content.
However, the energy dispersive X-ray fluorescence detection technique still has some disadvantages, which are mainly reflected in:
1. the X-ray power is low (generally only about 5-50W), the lower detection limit is not low enough, the sensitivity is not high enough, and the detection requirement of a low-content sample cannot be met;
2. The area of a sample detection area is small, and the sample representativeness is not ideal enough;
3. the accuracy and the repeatability of a detection result are slightly poor, and a plurality of positions need to be replaced for detection, so that the detection time of a sample is long, and the efficiency is low;
4. the settable detection parameters only comprise simple parameters such as optical filter selection, integration time and the like, and the method parameters are difficult to optimize aiming at different elements;
5. the calculation mode of the passivation result is unreasonable, and the actual passivation effect cannot be reflected without deducting the result of blank samples in the same batch.
Disclosure of Invention
Aiming at the defects, the invention provides the method for rapidly detecting the contents of titanium and zirconium in the aluminum alloy passivation film, which can realize the accurate and rapid detection of the contents of titanium and zirconium with low lower limit of sample detection, high sensitivity, good accuracy and repeatability, rapid detection, high detection efficiency and large detection area.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for quickly detecting the contents of titanium and zirconium in an aluminum alloy passive film,
the method is realized by using a wavelength dispersion type X-ray fluorescence spectrometer, and comprises the following steps:
s1, establishing a standard sample database;
s2, establishing a detection method;
S3, setting detection parameters;
s4, calibrating the detection method;
s5, verifying accuracy;
s6, detecting a sample;
and S7, calculating the result.
X-ray fluorescence analysis can be classified into two types, energy dispersion and wavelength dispersion, depending on the spectroscopic method. Aiming at the defects of the existing energy dispersion detection technology, the invention establishes a quantitative detection method for the contents of titanium and zirconium in the aluminum alloy passivation film on a wavelength dispersion type X-ray fluorescence spectrometer, and utilizes the characteristic of high power (several kW) of the wavelength dispersion type X-ray to realize the quantitative detection by using the wavelength dispersion type X-ray fluorescence spectrometer, and the method has the advantages of large detection area, representative sample, low lower detection limit of the sample, high sensitivity, good accuracy and repeatability, quick detection and high detection efficiency.
In a preferred embodiment of the present invention, the step S1 of establishing a standard sample database includes:
s11, preparing a plurality of standard samples of the aluminum alloy passive film containing Ti and Zr, wherein each standard sample has different contents, and the content ranges are respectively Ti: 1.0mg/m 2 ～100mg/m 2 ，Zr：0.4mg/m 2 ～100mg/m 2 ；
And S12, creating a standard sample database, and inputting the identification of each standard sample and the standard values of the corresponding Ti and Zr.
In a preferred technical solution of the present invention, the step S2 of establishing the detection method includes:
S21, establishing a new detection method, and customizing the name of the detection method;
and S22, adding element channels of Ti and Zr into the detection method.
In a preferred embodiment of the present invention, in the step S3, in setting the detection parameters, the set parameters include: set condition parameters, sample type and size, element settings, channel parameter settings, angle checks, calculated integration time, background mode, and pulse height selector checks.
In a preferred embodiment of the present invention, the step S3 of setting the detection parameters includes:
s31, setting condition parameters
Setting the analysis medium to be vacuum, setting the vacuum locking time to be a numerical value of 5-60 s, wherein the numerical value is used for pumping air brought into a vacuum system when a sample is replaced, setting the delay time to be a numerical value of 1-10 s, and selecting the model of a corresponding sample cup according to the configuration;
s32, sample type and size
Defining the sample type as a solid sample, and the sample size as one of fixed, variable or unknown;
s33, element setting
Respectively selecting Ti and Zr elements from the periodic table, setting the number of the plating layers to be 1, and setting the unit of the result to be mg/m 2 ；
S34, setting channel parameters
The channel parameters of Ti and Zr are set as follows:
Voltage, current: the voltage is one numerical value of 20-60 kV, the current is one numerical value of 10-160 mA, and the power does not exceed the maximum power allowed by the equipment;
analyzing a line: the analysis line is selected from one of KA, KB, LA, LB1 and LB 2;
spectroscopic crystal: the light splitting crystal selects one of Ge 111 or LiF 200;
a collimator: selecting one of 150 μm, 300 μm and 750 μm by the collimator;
a detector: the detector is set as one of a gas flow detector or a scintillation detector;
an optical filter: the filter is selected from one of Cu (400 μm), Al (750 μm), Al (200 μm) or no filter;
s35, angle checking
Placing a high-content standard sample into equipment to be measured, starting to run angle inspection, and recording an angle value obtained by scanning into a detection method by a system after the inspection is finished;
s36, calculating the integration time
After the angle check is finished, inputting the Ti and Zr concentrations of the standard samples, and enabling the standard samples to be used for detecting the Ti and Zr concentrations
The calculation result is input into an absolute error, and the system automatically calculates the Ti peak position integration time and the Zr peak position integration time and the background integration time respectively according to data and records the Ti peak position integration time and the Zr peak position integration time into a detection method; wherein C is the concentration of Ti and Zr in the standard sample;
s37 background mode
The background selects a single-point background mode, and the background calculation method selects one of a channel background, a calculation factor, a fixed factor, a polynomial and a null;
S38, pulse height selector check
And operating the checking function of the pulse height selector, and automatically calculating the upper and lower limit values of the pulse by the system and recording the upper and lower limit values into the detection method.
In a preferred embodiment of the present invention, the calibration of the detection method in step S4 includes:
s41, calling the established detection method, and selecting a standard sample according to the sample type;
s42, putting the series of standard samples into sample cups one by one and compacting the samples, wherein each standard sample is a sample cup, and the analysis software detects the standard samples in sequence according to the detection method parameters to obtain the signal intensity of each standard sample;
and S43, opening the detection method, associating the number of the detected standard sample with the detection method, and performing linear fitting on the signal intensity and the standard value of the Ti and Zr of the standard sample respectively to obtain a calibration working curve of the Ti and Zr, wherein the detection method is completed.
In a preferred embodiment of the present invention, the step S5 of verifying the accuracy includes:
and (3) taking the standard sample as an unknown sample, detecting by using a calibrated detection method, comparing a detection value with a standard value, and verifying the accuracy of the detection method.
In a preferred embodiment of the present invention, the step S6 of detecting the sample includes:
Shearing the passivated sample and the blank samples of the corresponding batches into the sizes suitable for the sample cups, then respectively filling the samples into different sample cups, selecting a calibrated detection method on an analysis interface, selecting an unknown sample as the sample type, and detecting by an instrument according to the set detection method to obtain the Ti and Zr contents of the passivated sample and the blank samples.
In a preferred embodiment of the present invention, the step S7 of calculating the result includes:
respectively subtracting the Ti content and the Zr content in the blank samples of the corresponding batches from the Ti content and the Zr content of the passivated samples to obtain the final passivation result, wherein the unit is mg/m 2 。
Compared with the prior art, the invention has the beneficial effects that: the method is realized by using the wavelength dispersion type X-ray fluorescence spectrometer by establishing the quantitative detection method of the titanium and zirconium contents in the aluminum alloy passivation film on the wavelength dispersion type X-ray fluorescence spectrometer by utilizing the characteristic of high power of the wavelength dispersion type X-ray, and the method has the advantages of large detection area, more representative sample, low lower detection limit of the sample, high sensitivity, good accuracy and repeatability, quick detection and high detection efficiency.
The invention establishes a quantitative detection method of titanium and zirconium content in the aluminum alloy passivation film on a wavelength dispersion type X-ray fluorescence spectrometer, sets and optimizes detection parameters such as voltage, current, analysis lines, spectroscopic crystals, a collimator, a detector, integration time, an optical filter and the like, calibrates the detection method by using a titanium and zirconium passivation film standard sample to obtain a calibration working curve, can simultaneously respectively load a plurality of batches of blank samples and a plurality of batches of passivation samples into different sample cups, detects by using an instrument according to a set program, and finally subtracts the result of the corresponding blank sample from the result of the passivation sample to obtain the accurate content of titanium and zirconium in the passivation film. The method is rapid and accurate, the lower limit of sample detection is low, the sensitivity is high, the accuracy and the repeatability are good, the detection area is large, and the sample is more representative. The invention can better reflect the actual effect of passivation and provide reliable basis for the evaluation and adjustment of the production process and the performance judgment of products.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below.
FIG. 1 is a flow chart of an embodiment of the present invention.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1, the invention provides a method for rapidly detecting the contents of titanium and zirconium in an aluminum alloy passivation film, which is implemented by using a wavelength dispersion type X-ray fluorescence spectrometer, and comprises the following steps:
s1, establishing a standard sample database, including:
s11, preparing a plurality of standard samples of the aluminum alloy passive film containing Ti and Zr, wherein each standard sample has different contents, and the content ranges are respectively Ti: 1.0mg/m 2 ～100mg/m 2 ，Zr：0.4mg/m 2 ～100mg/m 2 。
And S12, creating a standard sample database, and inputting the identification of each standard sample and the standard values of the corresponding Ti and Zr.
S2, establishing a detection method, which comprises the following steps:
and S21, establishing a new detection method and customizing the name of the detection method.
And S22, adding element channels of Ti and Zr into the detection method.
S3, setting detection parameters, including:
s31, setting condition parameters
The analysis medium is set to be vacuum, the vacuum locking time is set to be a numerical value of 5-60 s and used for pumping air brought into a vacuum system when a sample is replaced, the delay time is a numerical value of 1-10 s, and the model of the corresponding sample cup is selected according to the configuration.
S32, sample type and size
The sample type is defined as solid sample, and the sample size is one of fixed, variable, or unknown.
S33, element setting
Respectively selecting Ti and Zr elements from the periodic table, setting the number of the plating layers to be 1, and setting the unit of the result to be mg/m 2 。
S34, setting channel parameters
The channel parameters of Ti and Zr are set as follows:
voltage, current: the voltage is one value of 20-60 kV, the current is one value of 10-160 mA, and the power does not exceed the maximum power allowed by the equipment. The X-ray light pipe is used for exciting characteristic spectral lines of elements in a sample, and the voltage and the current determine the intensity of X-rays emitted by the X-ray light pipe. Different voltages and currents can be set depending on the excitation potentials of the different elements. To protect the X-ray tube, the power of the different elements is preferably equal.
Analyzing a line: the analytical line is selected from one of KA, KB, LA, LB1 and LB 2. Different analysis lines have different excitation efficiencies and are selected according to actual needs.
Spectroscopic crystal: the light splitting crystal selects one of Ge 111 or LiF 200. The function of the light splitting crystal is to separate X-rays with different wavelengths through a crystal diffraction phenomenon, and the light splitting crystal is a core component for obtaining a characteristic spectral line of an element to be detected, and the selection of the light splitting crystal is particularly important for the accuracy and reliability of an analysis result.
A collimator: the collimator selects one of 150 μm, 300 μm, and 750 μm. The collimator is composed of a plurality of metal sheets and has the function of converging divergent light into a beam of parallel light. The foil spacing affects the collimation, resolution and intensity of the beam. The smaller the foil pitch, the higher the collimation of the beam and the better the resolution, but the lower the intensity. The intensity and resolution performance of incident light need to be considered comprehensively.
A detector: the detector is set as one of a gas flow detector or a scintillation detector. The detector receives X-ray photons with a certain wavelength after light splitting, converts photon signals into electric signals, obtains the intensity value of X-ray fluorescence, and calculates the concentration of elements corresponding to the wavelength. The detector is divided into a gas flow detector and a scintillation detector, wherein the gas flow detector is mainly used for detecting the X-ray fluorescence of light elements, and the scintillation detector is mainly used for detecting the X-ray fluorescence of heavy elements.
An optical filter: the filter is selected from Cu (400 μm), Al (750 μm), Al (200 μm) or no filter. The optical filter is used for eliminating the characteristic line interference of the X-ray light tube target, inhibiting impurity spectrums harmful to analysis in the X-ray light tube spectrums, and improving the analysis sensitivity and accuracy.
And it can be understood that in the S34 channel parameter setting, in each parameter item and specific parameter, the setting range of the relevant parameter of Ti and Zr is the same, but the specific parameter value is set according to the actual requirement, and the specific parameter value of the relevant parameter of Ti and Zr may be the same or different.
S35, angle checking
The angle check is used to determine the actual angle (2 θ angle) of each element. And (3) placing a high-content standard sample into equipment to be measured, starting to run angle inspection, and recording the angle value obtained by scanning into the detection method by the system after the inspection is finished.
S36, calculating the integration time
After the angle check is finished, inputting the Ti and Zr concentrations of the standard samples, and enabling the standard samples to be used for detecting the Ti and Zr concentrations
The calculation result is input into an absolute error, and the system automatically calculates the Ti peak position integration time and the Zr peak position integration time and the background integration time respectively according to data and records the Ti peak position integration time and the Zr peak position integration time into a detection method; wherein, C is the Ti and Zr concentration of the standard sample.
S37, background mode
The background selects a single-point background mode, and the background calculation method selects one of a channel background, a calculation factor, a fixed factor, a polynomial and a null.
S38 pulse height selector (PHD) check
The pulse height selector (PHD) is mainly used for filtering the signal intensity generated by the noise caused by low-voltage noise and current fluctuation, only the pulse falling between the set upper level discrimination and the set lower level discrimination (namely the set upper limit and the set lower limit) passes through the counting circuit, unnecessary pulses are eliminated, the interference is reduced, the background intensity is reduced, and the sensitivity is improved. And operating the checking function of the pulse height selector, and automatically calculating the upper and lower limit values of the pulse by the system and recording the upper and lower limit values into the detection method.
And after the detection parameter setting is finished, the method is saved and quit.
S4, calibrating the detection method, including:
and S41, calling the established detection method, and selecting the standard sample from the sample types.
S42, placing the series of standard samples into sample cups one by one, compacting the samples by using plastic compression rings, wherein each standard sample is a sample cup, and the analysis software detects the standard samples in sequence according to the detection method parameters to obtain the signal intensity of each standard sample.
And S43, opening the detection method, associating the number of the detected standard sample with the detection method, and performing linear fitting on the signal intensity and the standard value of the Ti and Zr of the standard sample respectively by using the calibration function of the analysis software to obtain the calibration working curve of the Ti and Zr, so that the detection method is calibrated.
S5, accuracy verification
And (3) taking the standard sample as an unknown sample, detecting by using a calibrated detection method, comparing a detection value with a standard value, and verifying the accuracy of the detection method. The detection method after calibration and verification can be repeatedly used without establishing the method every time.
S6, detecting the sample
Since the aluminum alloy itself contains a certain amount of Ti and Zr, which do not come from the passivation step, the sample before passivation is referred to as a blank sample. The blank is not the same for each batch, so the blank sample is tested along with the batch of passivated sample. Shearing the passivated sample and the blank samples of the corresponding batches into the sizes suitable for the sample cups by using a plate shearing machine, then respectively filling the samples into different sample cups, selecting a calibrated detection method on an analysis interface, selecting an unknown sample as a sample type, and detecting by using an instrument according to a set detection method to obtain the Ti and Zr contents of the passivated sample and the blank samples.
S7, calculating the result
Respectively subtracting the Ti content and the Zr content in the blank samples of the corresponding batches from the Ti content and the Zr content of the passivated samples to obtain the final passivation result, wherein the unit is mg/m 2 。
It will be appreciated that the wavelength dispersive X-ray fluorescence spectrometer used must have the functionality required for use in the method steps employed in the present invention.
In order to achieve a clearer explanation of the present invention, the following are more specific examples of the present invention.
Example 1
The preferred embodiment provides a method for rapidly detecting the contents of titanium and zirconium in an aluminum alloy passive film, which is used for detecting the contents of the titanium and the zirconium in a 6016 aluminum alloy passive film and is realized by using a wavelength dispersion type X-ray fluorescence spectrometer, and comprises the following steps:
s1, establishing a standard sample database
S11, preparing 6 standard samples of the passivation film of the 6XXX aluminum alloy containing Ti and Zr, wherein each standard sample has different contents, and the content ranges are respectively Ti: 1.0mg/m 2 ～30.5mg/m 2 ，Zr：0.5mg/m 2 ～34.0mg/m 2 。
S12, creating a standard sample database, and inputting a database name: the method comprises the steps of inputting standards (6 XXX-1-6 XXX-6) of 6XXX Ti and Zr of standard samples, and inputting standard values of the Ti and the Zr corresponding to the standard samples.
S2 establishing detection method
S21, establishing a new detection method, and inputting the method names of 6XXX Ti and Zr at the self-defined detection method name.
S22, adding the element channels of Ti and Zr into the detection method through the function of channel addition.
S3, setting detection parameters
S31, setting condition parameters
The analysis medium was set to vacuum, the vacuum lock time was set to 6s, the delay time was 1s, and the sample cup model was selected to be 27mm steel.
S32, sample type and size
The sample type is defined as solid, and the sample size is fixed.
S33, element setting
Respectively selecting Ti and Zr elements from the periodic table, setting the number of the plating layers to be 1, and setting the unit of the result to be mg/m 2 。
S34, setting channel parameters
The channel parameters for Ti are set as:
voltage, current: the voltage was 40kV and the current was 50mA, at which time the power was 2 kW.
Analyzing a line: and selecting KA by an analysis line.
Spectroscopic crystal: the spectrometer crystal selects Ge 111.
A collimator: the collimator is chosen to be 150 μm.
A detector: the detector is set as a gas flow detector.
An optical filter: the filter was made of Al (200 μm).
The channel parameters of Zr are set as follows:
voltage, current: the voltage was 50kV and the current was 40mA, at which time the power was 2 kW.
Analyzing a line: the analysis line selects KB.
Spectroscopic crystal: LiF 200 is selected as the spectroscopic crystal.
A collimator: the collimator is chosen to be 300 μm.
A detector: the detector is set as a scintillation detector.
An optical filter: the filter was made of Al (200 μm).
S35, angle checking
And (4) placing a standard sample with the number of 6XXX-6 into the equipment to be measured, starting to run an angle check, and recording the angle value obtained by scanning into a detection method by the system after the check is finished.
S36, calculating the integration time
After the angle check is finished, inputting the Ti and Zr concentrations of the standard samples, and enabling the standard samples to be used for detecting the Ti and Zr concentrations
(wherein C is the concentration of Ti and Zr in the standard sample) is input into an absolute error, and the system automatically calculates the peak integration time and the background integration time of Ti and Zr according to the data, respectively: ti is 100s, Zr is 110 s; background integration time: ti is 10s and Zr is 20 s.
S37 background mode
The Ti and Zr backgrounds are selected from a single-point background mode, and the calculation methods of the backgrounds are selected from calculation factors.
S38 pulse height selector (PHD) check
And (3) operating a pulse height selector (PHD) checking function, and automatically calculating the upper and lower pulse limit values by the system and recording the upper and lower pulse limit values into the detection method.
And after the detection parameter setting is finished, the method is saved and quit.
S4, calibration of detection method
S41, calling the established detection method of 6XXX Ti and Zr, and selecting the sample type of the standard sample.
S42, putting 6 standard samples numbered 6 XXX-1-6 XXX-6 into sample cups one by one, compacting the standard samples by a plastic compression ring, and sequentially detecting the standard samples by analysis software according to the detection method parameters to obtain the signal intensity of each standard sample.
S43, opening a detection method of 6XXX Ti and Zr, associating the serial numbers 6 XXX-1-6 XXX-6 of the detected standard samples with the detection method, respectively carrying out linear fitting on the Ti and Zr signal intensities and the standard values of the 6 XXX-1-6 XXX-6 standard samples by using the self calibration function of analysis software, respectively obtaining calibration working curves of Ti and Zr, and completing the calibration of the detection method. The linear correlation coefficients of the Ti and Zr calibration working curves are respectively R 2 ＝0.9996，R 2 0.9997, indicating good linearity.
S5, accuracy verification
The standard sample was used as an unknown sample, and the Ti content was 10.2mg/m 2 Zr content 8.1mg/m 2 The standard sample of (2) was verified to have a verification value of Ti 10.1mg/m 2 、Zr 8.2mg/m 2 The method is accurate and reliable.
S6, detecting the sample
Respectively shearing a No. 1 passivated sample with an alloy grade of 6016 and a corresponding batch blank sample into blocks of 35mm x 35mm by using a plate shearing machine, then respectively filling the blocks into different sample cups, selecting a calibrated detection method ' 6XXX Ti and Zr ' on an analysis interface, selecting an unknown sample ' in a sample type, and detecting by using an instrument according to a set detection method to obtain that the No. 1 passivated sample Ti is 14.8mg/m 2 Zr is 15.2mg/m 2 The blank sample had Ti of 5.3mg/m 2 Zr is 0.5mg/m 2 。
S7, calculating the result
Subtracting the result of the corresponding blank sample from the result of the passivation sample to obtain the 6016 aluminum alloy No. 1 passivation sample passivation film with the accurate contents of titanium and zirconium respectively as Ti: 14.8-5.3 ═ 9.5mg/m 2 ，Zr：15.2-0.5＝14.7mg/m 2 。
Example 2
The preferred embodiment provides a method for rapidly detecting the contents of titanium and zirconium in an aluminum alloy passivation film, which is used for detecting the contents of the titanium and the zirconium in a 5754 aluminum alloy passivation film and is realized by using a wavelength dispersion type X-ray fluorescence spectrometer, and comprises the following steps:
s1, establishing a standard sample database
S11, preparing 8 standard samples of 5XXX aluminum alloy passivation films containing Ti and Zr, wherein each standard sample has different contents, and the content ranges are respectively Ti: 2.0mg/m 2 ～61.2mg/m 2 ，Zr：0.4mg/m 2 ～100.0mg/m 2 。
S12, creating a standard sample database, and inputting a database name: 5XXX Ti and Zr standard samples, inputting the marks (5XXX-1 to 5XXX-8) of the standard samples, and inputting the standard values of the Ti and the Zr corresponding to the standard samples.
S2 establishing detection method
S21, establishing a new detection method, and inputting the method names of 5XXX Ti and Zr at the self-defined detection method name.
S22, adding the element channels of Ti and Zr into the detection method through the function of channel addition.
S3, setting detection parameters
S31, setting condition parameters
The analysis medium was set to vacuum, the vacuum lock time was set to 8s, the delay time was 4s, and the sample cup model was selected to be 27mm steel.
S32, sample type and size
The sample type is defined as solid, and the sample size is fixed.
S33, element setting
Respectively selecting Ti and Zr elements from the periodic table, setting the number of the plating layers to be 1, and setting the unit of the result to be mg/m 2 。
S34, setting channel parameters
The channel parameters for Ti are set as:
voltage, current: the voltage was 50kV and the current was 60mA, at which time the power was 3 kW.
Analyzing a line: and selecting KA by an analysis line.
Spectroscopic crystal: LiF 200 is selected as the spectroscopic crystal.
A collimator: the collimator is chosen to be 300 μm.
A detector: the detector is set as a gas flow detector.
An optical filter: the filter is selected to be "none".
The channel parameters of Zr are set as follows:
voltage, current: the voltage was 60kV and the current was 50mA, at which time the power was 3 kW.
Analyzing a line: the analysis line selects KB.
Spectroscopic crystal: LiF 200 is selected as the spectroscopic crystal.
A collimator: the collimator is chosen to be 300 μm.
A detector: the detector is set as a scintillation detector.
An optical filter: the filter is selected to be "none".
S35, angle checking
And (3) placing the standard sample with the number of 5XXX-5 into equipment to be measured, starting to run an angle check, and recording the angle value obtained by scanning into a detection method by the system after the check is finished.
S36, calculating the integration time
After the angle check is finished, inputting the Ti and Zr concentrations of the standard samples, and enabling the standard samples to be used for detecting the Ti and Zr concentrations
(wherein C is the concentration of Ti and Zr in the standard sample) is input into an absolute error, and the system automatically calculates the peak integration time and the background integration time of Ti and Zr according to the data, respectively: ti is 90s, Zr is 105 s; background integration time: ti is 8s and Zr is 12 s.
S37 background mode
The Ti and Zr backgrounds are selected from a single-point background mode, and the calculation methods of the backgrounds are selected from calculation factors.
S38 pulse height selector (PHD) check
And (3) operating a pulse height selector (PHD) checking function, and automatically calculating the upper and lower pulse limit values by the system and recording the upper and lower pulse limit values into the detection method.
And after the detection parameter setting is finished, the method is saved and quit.
S4, calibration of detection method
S41, calling the established detection method of 5XXX Ti and Zr, and selecting the sample type of the standard sample.
S42, putting 8 standard samples numbered as 5 XXX-1-5 XXX-8 into sample cups one by one, compacting the standard samples by a plastic compression ring, and sequentially detecting the standard samples by analysis software according to the detection method parameters to obtain the signal intensity of each standard sample.
S43, opening the detection method of 5XXX Ti and Zr, numbering the detected standard sampleAnd (5) correlating 5 XXX-1-5 XXX-8 with the detection method, and performing linear fitting on the Ti and Zr signal intensities and the standard values of the 5 XXX-1-5 XXX-8 standard samples by using a calibration function carried by analysis software to obtain a calibration working curve of Ti and Zr, so that the detection method is calibrated. The linear correlation coefficients of the Ti and Zr calibration working curves are respectively R 2 ＝0.9995，R 2 0.9994, indicating good linearity.
S5, accuracy verification
The standard sample was used as an unknown sample, and the Ti content was 40.5mg/m 2 Zr content 46.1mg/m 2 The standard sample of (2) was verified to have a verification value of Ti 40.1mg/m 2 、Zr 46.4mg/m 2 The method is accurate and reliable.
S6, detecting the sample
Respectively shearing a 2# passivated sample with an alloy mark of 5754 and a corresponding batch of blank samples into blocks of 37mm x 37mm by using a plate shearing machine, then respectively filling the blocks into different sample cups, selecting calibrated detection methods '5 XXX Ti and Zr' on an analysis interface, selecting an 'unknown sample' in a sample type, and detecting by using an instrument according to a set detection method to obtain that the Ti content of the 2# passivated sample is 30.5mg/m 2 Zr 84.0mg/m 2 The blank sample had Ti of 15.6mg/m 2 Zr 11.8mg/m 2 。
S7, calculating the result
Subtracting the result of the corresponding blank sample from the result of the passivated sample to obtain the passivating film of the 5754 aluminum alloy No. 2 passivated sample, wherein the accurate contents of titanium and zirconium are respectively Ti: 30.5-15.6 ═ 14.9mg/m 2 ，Zr：84.0-11.8＝72.2mg/m 2 。
Example 3
The preferred embodiment provides a method for rapidly detecting the contents of titanium and zirconium in an aluminum alloy passive film, which is used for detecting the contents of the titanium and the zirconium in a 5182 aluminum alloy passive film and is realized by using a wavelength dispersion type X-ray fluorescence spectrometer, and comprises the following steps:
s1, establishing a standard sample database
S11, preparing 12 5XXX&6XXX aluminum alloy passive film standard samples, each standard sampleThe product has different contents, wherein the content ranges are respectively Ti: 1.0mg/m 2 ～61.2mg/m 2 ，Zr：0.4mg/m 2 ～100.0mg/m 2 。
S12, creating a standard sample database, and inputting a database name: 5XXX &6XXX Ti and Zr standard samples, inputting the mark (5XXX &6XXX-1 to 5XXX &6XXX-12) of each standard sample, and inputting the standard value of each standard sample corresponding to Ti and Zr.
S2 establishing detection method
S21, establishing a new detection method, and inputting the method name of 5XXX &6XXX Ti, Zr at the name of the self-defined detection method.
S22, adding the element channels of Ti and Zr into the detection method through the function of channel addition.
S3, setting detection parameters
S31, setting condition parameters
The analysis medium was set to vacuum, the vacuum lock time was set to 5s, the delay time was 2s, and the sample cup type was selected to be 27mm steel.
S32, sample type and size
The sample type is defined as solid, and the sample size is fixed.
S33, element setting
Respectively selecting Ti and Zr elements from the periodic table, setting the number of the plating layers to be 1, and setting the unit of the result to be mg/m 2 。
S34, setting channel parameters
The channel parameters for Ti are set as:
voltage, current: the voltage was 50kV and the current was 60mA, at which time the power was 3 kW.
Analyzing a line: and selecting KA by an analysis line.
Spectroscopic crystal: LiF 200 is selected as the spectroscopic crystal.
A collimator: the collimator is chosen to be 300 μm.
A detector: the detector is set as a gas flow detector.
An optical filter: the filter is selected to be "none".
The channel parameters of Zr are set as follows:
voltage, current: the voltage was 60kV and the current was 50mA, at which time the power was 3 kW.
Analyzing a line: and selecting KA by an analysis line.
Spectroscopic crystal: LiF 200 is selected as the spectroscopic crystal.
A collimator: the collimator is chosen to be 300 μm.
A detector: the detector is set as a scintillation detector.
An optical filter: the filter is selected to be "none".
S35, angle checking
And (3) placing a standard sample with the number of 5XXX &6XXX-7 into the equipment to be measured, starting to run an angle check, and recording the angle value obtained by scanning into a detection method by the system after the check is finished.
S36, calculating the integration time
After the angle check is finished, inputting the Ti and Zr concentrations of the standard samples, and enabling the standard samples to be used for detecting the Ti and Zr concentrations
(wherein C is the concentration of Ti and Zr in the standard sample) is input into an absolute error, and the system automatically calculates the peak integration time and the background integration time of Ti and Zr according to the data, respectively: ti is 130s, Zr is 130 s; background integration time: ti is 13s and Zr is 13 s.
S37 background mode
The Ti and Zr backgrounds are selected from a single-point background mode, and the calculation methods of the backgrounds are selected from calculation factors.
S38 pulse height selector (PHD) check
And (3) operating a pulse height selector (PHD) checking function, and automatically calculating the upper and lower pulse limit values by the system and recording the upper and lower pulse limit values into the detection method.
And after the detection parameter setting is finished, the method is saved and quit.
S4, calibration of detection method
S41, calling the established detection method of 5XXX &6XXX Ti, Zr, and selecting the sample type of the standard sample.
S42, putting 12 standard samples with the serial numbers of 5XXX &6 XXX-1-5 XXX &6XXX-12 into sample cups one by one, pressing each standard sample cup by a plastic compression ring, and sequentially detecting the standard samples by analysis software according to the detection method parameters to obtain the signal intensity of each standard sample.
S43, opening detection method 5XXX&6XXX Ti, Zr', Standard sample No. 5XXX to complete detection&6XXX-1～5XXX&6XXX-12 is associated with the detection method, and 5XXX is respectively detected by using the calibration function carried by the analysis software&6XXX-1～5XXX&And performing linear fitting on the Ti and Zr signal intensities and the standard values of the 6XXX-12 standard sample to obtain a Ti and Zr calibration working curve, and completing the calibration of the detection method. The linear correlation coefficients of the Ti and Zr calibration working curves are respectively R 2 ＝0.9997，R 2 Indicating good linearity at 0.9996.
S5, accuracy verification
A certain standard sample is taken as an unknown sample, and the Ti content is 28.3mg/m 2 Zr content 18.2mg/m 2 The standard sample of (2) was verified to have a verification value of Ti 28.2mg/m 2 、Zr 18.1mg/m 2 The difference between the verification value and the standard value is very small, and the relative errors of Ti and Zr are respectively 0.35% and 0.55%, which shows that the detection method is accurate and reliable.
In order to examine the detection limit of this method, the detection was repeated 10 times using a blank sample, and the detection results are shown in Table 1, wherein 3 times the standard deviation of the blank sample was used as the detection limit, and the detection limit of Ti was 0.10mg/m 2 Zr detection limit 0.20mg/m 2 。
TABLE 1 detection Limit test results
| Serial number | Ti(mg/m 2 ) | Zr(mg/m 2 ) |
| 1 | 3.1 | 0.8 |
| 2 | 3.1 | 0.7 |
| 3 | 3.1 | 0.7 |
| 4 | 3.1 | 0.7 |
| 5 | 3.0 | 0.6 |
| 6 | 3.1 | 0.8 |
| 7 | 3.1 | 0.8 |
| 8 | 3.1 | 0.7 |
| 9 | 3.1 | 0.8 |
| 10 | 3.1 | 0.7 |
| Mean value of | 3.09 | 0.73 |
| Standard deviation of | 0.0316 | 0.0675 |
| Detection limit | 0.10 | 0.20 |
To examine the reproducibility of the method, the test was repeated 10 times using a certain passivated sample, and the test results are shown in table 2. As can be seen from the results, the relative standard deviation of Ti was 0.36%, and the relative standard deviation of Zr was 0.83%. The relative standard deviation is very small, which shows that the established detection method has good repeatability.
TABLE 2 results of the repeatability tests
S6, detecting sample
Cutting 3# passivated sample with alloy number 5182 and corresponding blank sample into blocks of 36mm by using a plate shearing machine, respectively filling the blocks into different sample cups, and selecting a calibrated detection method '5 XXX' on an analysis interface&6XXX Ti and Zr', the sample type is selected from unknown sample, the instrument is used for detection according to the set detection method, and the measured 3# passivated sample Ti is 7.9mg/m 2 Zr is 6.3mg/m 2 The blank sample had Ti of 5.3mg/m 2 Zr is 2.1mg/m 2 。
S7, calculating the result
Subtracting the result of the corresponding blank sample from the result of the passivation sample to obtain the titanium and zirconium contents in the passivation film, wherein the titanium and zirconium contents are respectively Ti: 7.9-5.3 ═ 2.6mg/m 2 ，Zr：6.3-2.1＝4.2mg/m 2 。
In order to better represent the technical difference between the invention and the prior art, the main parameters of example 3 of the invention are compared with the zirconium-titanium content of 6016 aluminum alloy passivation film measured by X-ray fluorescence spectrometry (referred to as prior art 1 hereinafter) and the zirconium content of a metal material surface conversion film disclosed by CN110243810A (referred to as prior art 2 hereinafter), and the comparison is specifically shown in Table 3. The biggest difference is that the type of equipment used in the invention is wavelength dispersive, the X-ray power and current are high, and the used collimator, detector and the like are different.
Table 3 parameter comparison of example 3 with prior art 1 and prior art 2
The difference in the main detection performance between example 3 of the present invention and prior art 1 and prior art 2 is shown in table 4.
Table 4 comparison of the detection performance of example 3 of the present invention with that of prior art 1 and prior art 2
As can be seen from Table 4, the outstanding detection performance advantages of example 3 of the present invention are represented by lower relative error, lower detection limit (only 1/6 corresponding to the value), higher sensitivity, wider upper and lower limits of the standard sample content, and better detection repeatability, compared with the prior art 1. In addition, prior art 1 has a sample detection area of only about 20mm due to the limitation of the size of the X-ray excitation window of the device 2 More than 5 positions are required for each sampleThe detection takes a long time. The sample detection area of the invention reaches 572mm 2 The detection result of the sample is more representative and has good repeatability because the detection result is more than 20 times that of the prior art 1, and each sample only needs to be detected once, so that the detection efficiency is improved.
Compared with the prior art 2, the method has the outstanding detection performance advantages that one more Ti element is added as a detection element, the linear correlation coefficient is better, the detection limit is very low (only 1/86 of the corresponding numerical value), the sensitivity is higher, the lower limit of the content of the standard sample is lower, and the method is more suitable for the actual detection situation of the aluminum alloy (in many cases, the blank sample and the sample content are less than the lower limit Zr of the detection in the prior art 2: 17.31 mg/m) 2 ) The detection repeatability is also better than that of the prior art 2. In addition, even though the aluminum alloy sample (referred to as blank sample) which is not passivated also contains Ti and Zr, and the blank sample content of each batch is different, the blank samples of the same batch are not detected and the content of the blank samples is deducted in the prior art 2, and the obtained value is not only of the passivation process, but also contains the value of the aluminum alloy itself, and cannot reflect the actual passivation effect, so the actual passivation effect can be reflected more reasonably by the method.
In conclusion, the rapid detection method for the contents of titanium and zirconium in the aluminum alloy passivation film has lower detection limit (Ti is 0.10 mg/m) 2 Zr 0.20mg/m 2 ) The accuracy and the repeatability are better (the relative standard deviation is less than 1 percent), and the detected area of the sample is larger (more than 500 mm is achieved) 2 ) The method has the advantages that the representativeness of the samples is better, the detection result can be obtained by each sample within about 5min, the detection efficiency is higher, the actual passivation effect can be better reflected, and reliable basis is provided for the evaluation and adjustment of the production process and the performance judgment of the product.
The method is realized by using the wavelength dispersion type X-ray fluorescence spectrometer by establishing the quantitative detection method of the titanium and zirconium contents in the aluminum alloy passivation film on the wavelength dispersion type X-ray fluorescence spectrometer by utilizing the characteristic of high power of the wavelength dispersion type X-ray, and the method has the advantages of large detection area, more representative sample, low lower detection limit of the sample, high sensitivity, good accuracy and repeatability, quick detection and high detection efficiency.
The invention establishes a quantitative detection method of titanium and zirconium content in the aluminum alloy passivation film on a wavelength dispersion type X-ray fluorescence spectrometer, sets and optimizes detection parameters such as voltage, current, analysis lines, spectroscopic crystals, a collimator, a detector, integration time, an optical filter and the like, calibrates the detection method by using a titanium and zirconium passivation film standard sample to obtain a calibration working curve, can simultaneously respectively load a plurality of batches of blank samples and a plurality of batches of passivation samples into different sample cups, detects by using an instrument according to a set program, and finally subtracts the result of the corresponding blank sample from the result of the passivation sample to obtain the accurate content of titanium and zirconium in the passivation film. The method is rapid and accurate, has low lower limit of sample detection, high sensitivity, good accuracy and repeatability and large detection area, and ensures that the sample is more representative. The invention can better reflect the actual effect of passivation and provide reliable basis for evaluation and adjustment of the production process and performance judgment of products.
The above description is only for the specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (9)
1. A method for rapidly detecting the contents of titanium and zirconium in an aluminum alloy passive film is characterized in that,
the method is realized by using a wavelength dispersion type X-ray fluorescence spectrometer, and comprises the following steps:
s1, establishing a standard sample database;
s2, establishing a detection method;
s3, setting detection parameters;
s4, calibrating the detection method;
s5, verifying accuracy;
s6, detecting a sample;
and S7, calculating the result.
2. The method for rapidly detecting the contents of titanium and zirconium in the aluminum alloy passivation film according to claim 1, characterized in that,
the step S1 of building a standard sample database includes:
s11, preparing a plurality of standard samples of the aluminum alloy passive film containing Ti and Zr, wherein each standard sample has different contents, and the content ranges are respectively Ti: 1.0 mg/m 2 ~100 mg/m 2 ，Zr：0.4 mg/m 2 ~100 mg/m 2 ；
And S12, creating a standard sample database, and inputting the identification of each standard sample and the standard values of the corresponding Ti and Zr.
3. The method for rapidly detecting the contents of titanium and zirconium in the aluminum alloy passivation film according to claim 1, characterized in that,
the step S2 is to establish a detection method, including:
s21, establishing a new detection method, and customizing the name of the detection method;
and S22, adding element channels of Ti and Zr into the detection method.
4. The method for rapidly detecting the contents of titanium and zirconium in the aluminum alloy passivation film according to claim 1, characterized in that,
in the step S3, in setting the detection parameters, the set parameters include: set condition parameters, sample type and size, element settings, channel parameter settings, angle checks, calculated integration time, background mode, and pulse height selector checks.
5. The method for rapidly detecting the contents of titanium and zirconium in the aluminum alloy passivation film according to claim 1 or 4,
the step S3 sets detection parameters, including:
s31, setting condition parameters
Setting the analysis medium to be vacuum, setting the vacuum locking time to be a numerical value of 5-60 s, wherein the numerical value is used for pumping air brought into a vacuum system when a sample is replaced, setting the delay time to be a numerical value of 1-10 s, and selecting the model of a corresponding sample cup according to the configuration;
s32, sample type and size
Defining the sample type as a solid sample, and the sample size as one of fixed, variable or unknown;
s33, element setting
Respectively selecting Ti and Zr elements from the periodic table, setting the number of the plating layers to be 1, and setting the unit of the result to be mg/m 2 ；
S34, setting channel parameters
The channel parameters of Ti and Zr are set as follows:
voltage, current: the voltage is one numerical value of 20-60 kV, the current is one numerical value of 10-160 mA, and the power does not exceed the maximum power allowed by the equipment;
analyzing a line: the analysis line is selected from one of KA, KB, LA, LB1 and LB 2;
spectroscopic crystal: the light splitting crystal selects one of Ge 111 or LiF 200;
a collimator: selecting one of 150 μm, 300 μm and 750 μm for the collimator;
a detector: the detector is set as one of a gas flow detector or a scintillation detector;
an optical filter: the filter is selected from one of Cu (400 μm), Al (750 μm), Al (200 μm) or no filter;
s35, angle checking
Placing a high-content standard sample into equipment to be measured, starting to run angle inspection, and recording an angle value obtained by scanning into a detection method by a system after the inspection is finished;
s36, calculating the integration time
After the angle check is finished, the Ti and Zr concentrations of the standard sample are input, and 0.005 x
The calculation result is input into 'absolute error', and the system automatically calculates the peak positions of Ti and Zr according to the data respectivelyIntegrating time and background integrating time, and recording the integrating time and the background integrating time into a detection method; wherein C is the concentration of Ti and Zr in the standard sample;
S37, background mode
Selecting a single-point background mode as a background, and selecting one of a channel background, a calculation factor, a fixed factor, a polynomial and a null according to a background calculation method;
s38, pulse height selector check
And operating the checking function of the pulse height selector, and automatically calculating the upper and lower limit values of the pulse by the system and recording the upper and lower limit values into the detection method.
6. The method for rapidly detecting the contents of titanium and zirconium in the aluminum alloy passivation film according to claim 1, characterized in that,
the step S4 of calibrating the detection method includes:
s41, calling the established detection method, and selecting a standard sample according to the sample type;
s42, putting the series of standard samples into sample cups one by one and compacting the samples, wherein each standard sample is a sample cup, and the analysis software detects the standard samples in sequence according to the detection method parameters to obtain the signal intensity of each standard sample;
and S43, opening the detection method, associating the number of the detected standard sample with the detection method, and performing linear fitting on the signal intensity and the standard value of the Ti and Zr of the standard sample respectively to obtain a calibration working curve of the Ti and Zr, wherein the detection method is completed.
7. The method for rapidly detecting the contents of titanium and zirconium in the aluminum alloy passivation film according to claim 1, characterized in that,
The step S5 accuracy verification includes:
and (3) taking the standard sample as an unknown sample, detecting by using a calibrated detection method, comparing a detection value with a standard value, and verifying the accuracy of the detection method.
8. The method for rapidly detecting the contents of titanium and zirconium in the aluminum alloy passivation film according to claim 1, characterized in that,
the step S6 of detecting the sample includes:
shearing the passivated sample and the blank samples of the corresponding batches into the sizes suitable for the sample cups, then respectively filling the samples into different sample cups, selecting a calibrated detection method on an analysis interface, selecting an unknown sample as the sample type, and detecting by an instrument according to the set detection method to obtain the Ti and Zr contents of the passivated sample and the blank samples.
9. The method for rapidly detecting the contents of titanium and zirconium in the aluminum alloy passivation film according to claim 1, characterized in that,
the step S7 result calculation includes:
respectively subtracting the Ti content and the Zr content in the blank samples of the corresponding batches from the Ti content and the Zr content of the passivated samples to obtain the final passivation result, wherein the unit is mg/m 2 。
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