CN103901066B - A kind ofly obtain the method for standard dilution than lower x-ray fluorescence intensity - Google Patents

Abstract

The invention relates to a kind of standard dilution that obtains than the method for lower x-ray fluorescence intensity and application thereof.This acquisition standard dilution, than the method for lower x-ray fluorescence intensity, comprising: step 1, tested sample is prepared as bead, and the dilution ratio of this bead is R; Step 2, carries out X-fluorescence strength detection to the bead of above-mentioned preparation, obtains the X-fluorescence intensity level I of certain element in sample; Step 3, obtains standard dilution according to formulae discovery and compares R ₀under X-fluorescence intensity I ₀.Fluorescence intensity under adopting this method the fluorescence intensity of element under different dilution ratio can be converted into standard dilution ratio, thus be no longer limited to and quantitatively sample, greatly can improve analysis efficiency and reduce due to the sample resultant error that the reason such as moisture absorption causes in weighing process.<!--1-->

Description

A kind ofly obtain the method for standard dilution than lower x-ray fluorescence intensity

Technical field

The present invention relates to a kind of x-ray fluorescence analysis method, particularly relate to a kind of in x-ray fluorescence analysis, obtain x-ray fluorescence intensity under standard dilution ratio method and application thereof.

Background technology

X-ray fluorescence analysis method is a kind of quantitative analysis method based on existence function relation between tested element x-ray fluorescence intensity and concentration.Funtcional relationship between intensity and concentration is determined by adopting the method for standard model Criterion curve.

Before the x-ray fluorescence intensity of sample is measured in existing fusion method x-ray fluorescence analysis, first sample preparation will be become bead, in mother glass fuse piece, the calcination base mass ratio of flux and sample is called dilution ratio, is designated as R ₀.When measuring the x-ray fluorescence intensity of standard model, also first preparation of standard sample should be become bead, during preparation standard mother glass fuse piece, the calcination base mass ratio of flux and standard model is called standard dilution ratio, is designated as Rs.When preparing unknown sample bead, need the flux after to calcination and sample precise, to obtain the dilution ratio R more equal than Rs with standard dilution.Recorded the fluorescence intensity of element under this dilution ratio R by x-ray fluorescence analyzer, so carry out concentration ask calculation.But, existing fuse piece preparation method requires to carry out quantitatively precise to sample and flux, not only waste time and energy in weighing process, and easily owing to weighing inaccurate introducing experimental error, cause the dilution ratio of actual fuse piece to depart from standard dilution ratio, thus cause the accuracy of analysis result and precision poor.

Because the defect that above-mentioned existing x-ray fluorescence analysis method exists, through constantly research and experiment, finally create the present invention had practical value.

Summary of the invention

Fundamental purpose of the present invention is, there is provided a kind of and obtain the method for standard dilution than lower x-ray fluorescence intensity, technical matters to be solved is the fluorescence intensity under making it fluorescence intensity of element to be measured under different dilution ratio can be converted into standard dilution ratio, thus be no longer limited to and quantitatively sample, improve analysis efficiency, thus be more suitable for practicality.

The object of the invention to solve the technical problems realizes by the following technical solutions.Obtain the method for standard dilution than lower x-ray fluorescence intensity according to a kind of of the present invention's proposition, it comprises:

Step 1, is prepared as bead by tested sample, and the dilution ratio of this bead is R;

Step 2, carries out X-fluorescence strength detection to the bead of above-mentioned preparation, obtains the X-fluorescence intensity level I of certain element in sample;

Step 3, according to formula: calculate standard dilution and compare R ₀under X-fluorescence intensity I ₀, wherein α _i,ffor flux influence coefficient.

Preferably, above-mentioned acquisition standard dilution than the method for lower x-ray fluorescence intensity, described flux influence coefficient α _i,fobtained by once step,

Step S1, with flux and the multiple bead of tested sample preparation, each bead has different dilution ratio R;

Step S2, carries out x-ray fluorescence intensity mensuration to above-mentioned each bead, obtains the x-ray fluorescence intensity I of certain element i in each bead;

Step S3, if the concentration of element i is Ci in above-mentioned tested sample, crosses initial point with the concentration C i of element i to I and RI and does multiple linear regressive analysis, obtains two slopes and is designated as slope K 1 and slope K 2, then flux influence coefficient α _i,f=K2/K1.

Preferably, above-mentioned acquisition standard dilution is than the method for lower x-ray fluorescence intensity, and the dilution ratio R described in described step 1 is within the scope of 3-10.

Preferably, above-mentioned acquisition standard dilution is than the method for lower x-ray fluorescence intensity, and described tested sample is cement.

The present invention also proposes a kind of standard dilution that obtains and is measuring the application in cement sample than the method for lower x-ray fluorescence intensity.

The present invention also proposes a kind of measuring method of cement sample, its adopt above-mentioned acquisition standard dilution than the method for lower x-ray fluorescence intensity obtain standard dilution than under fluorescence intensity, and then the content of element in sample can be obtained by typical curve, thus complete the analysis of cement sample composition.

By technique scheme, the present invention establishes a kind of fluorescence intensity conversion method, fluorescence intensity under adopting this method the fluorescence intensity of element under different dilution ratio can be converted into standard dilution ratio, thus be no longer limited to and quantitatively sample, dilution ratio can change arbitrarily and can not the accuracy of impact analysis result within the specific limits, greatly can improve analysis efficiency and reduce due to the sample resultant error that the reason such as moisture absorption causes in weighing process.

Method of the present invention can be used in cement x-ray fluorescence analysis, show at the application result of national cement Product Quality Verification Centers, this technology has a good application prospect in cement production enterprise laboratory, and then is expected to become the indispensable technology that x-ray fluorescence analyzer device enters cement industry.

Above-mentioned explanation is only the general introduction of technical solution of the present invention, in order to better understand technological means of the present invention, and can be implemented according to the content of instructions, be described in detail as follows below with preferred embodiment of the present invention.

Embodiment

For further setting forth the present invention for the technological means reaching predetermined goal of the invention and take and effect, with preferred embodiment, a kind of standard dilution that obtains proposed according to the present invention is described in detail as follows than the method for lower x-ray fluorescence intensity and the embodiment of application thereof.

Flux influence coefficient α _i,fmeasuring principle

The loss on ignition of assumes samples is L, and sample weighting amount is m _s, flux quality is m _f, ignore the loss on ignition of flux, then dilution ratio R can calculate by formula (1):

$R=\frac{m_f}{m_s(1-L_s)}---\left(1\right)$

And the massfraction y of sample can calculate by formula (2) in print:

$y=\frac{1}{1+R}---\left(2\right).$

When not considering the enhancement effect between element, the intensity I of element i in sample _iwith concentration C _ithe available formula of relation (3) represents:

$I_i=K\&times;\frac{C_i}{{\mathrm{\&mu;}}_s^{*}}---\left(3\right),$

In formula, K is constant, μ _sfor the mass absorption coefficient of sample.

In sample, the massfraction of element i is C _i, in fuse piece, the massfraction of element i can be expressed as yC _i, because the mass absorption coefficient of material to X ray has additive property, according to formula (3), the intensity of the element i in fuse piece can represent with formula (4):

$I_i=K\&times;\frac{{\mathrm{yC}}_i}{{\mathrm{y\&mu;}}_s^{*}+(1-y){\mathrm{\&mu;}}_f^{*}}---\left(4\right),$

Wherein μ _ffor the mass absorption coefficient of flux.

Obtain after algebraically conversion is carried out to formula (4):

$C_i=\frac{{\mathrm{\&mu;}}_s^{*}}{K}I\&lsqb;1+(1-y)/y\frac{{\mathrm{\&mu;}}_f^{*}}{{\mathrm{\&mu;}}_s^{*}}\&rsqb;---\left(5\right).$

The ratio of the definition mass absorption coefficient of flux and the mass absorption coefficient of sample is flux influence coefficient, is designated as α _i,f, that is:

Order and formula (2) is substituted into formula (5), after arrangement:

C _i＝K'I[1+(1/y-1)α _i,f]＝K'I(1+Rα _i,f)(6)。

Formula (6) is rewritten as:

Ci＝K’*I+K’α _i,f*R*I

(7)。

In sample, the concentration C i of element i and the available formula of relation (7) of its x-ray fluorescence intensity I and dilution ratio R represent.

Order: K ₁=K ' (8)

K ₂＝K’α _i,f(9)

Formula (9) obtains divided by formula (8):

α _i,f＝K ₂/K ₁(10)

In a jth fuse piece, the fluorescence intensity of element i is designated as I _i,j;

Order: $\begin{array}{cc}C=\left(\begin{array}{c}{C}_1\\ C_2\\ ...\\ C_i\end{array}\right)& K=\left(\begin{array}{c}{K}_1\\ K_2\end{array}\right)\end{array}$

Then the matrix expression of the multiple regression equation of formula (7) is:

C＝KX(11)

K＝(X ^TX) ^-1X ^TC(12)

X ^tfor the transposed matrix of X, X ^-1for the inverse matrix of X.

Prepare the sample fuse piece of a series of different dilution ratio, instrument records its fluorescence intensity I.Use C _iinitial point is crossed to I and RI and does linear regression analysis, can RI be tried to achieve _icorresponding slope K ₂and I _icorresponding slope K ₁, can α be tried to achieve by formula (10) _i,f.

With Al ₂o ₃for example, calculate flux influence coefficient:

$\begin{array}{cc}C=\left(\begin{array}{c}100\\ 100\\ 100\\ 100\\ 100\\ 100\\ 100\\ 100\\ 100\\ 100\\ 100\\ 100\\ 100\\ 100\\ 100\end{array}\right)& X=\left(\begin{array}{cc}18.10& 183.09\\ 19.66& 179.86\\ 20.75& 178.28\\ 22.10& 176.87\\ 23.16& 174.17\\ 24.36& 172.56\\ 25.69& 172.07\\ \mathrm{26.52.}& 168.67\\ 28.72& 165.28\\ 28.00& 167.26\\ 29.76& 164.12\\ 31.72& 160.32\\ 34.24& 158.31\\ 36.19& 154.20\\ 37.52& 151.72\end{array}\right)\end{array}$

By formula (12), K=(X ^tx) ^-1x ^tc=(0.7510.473), i.e. K ₁=0.751, K ₂=0.473, α _i,f=K ₂/ K ₁=0.630.The flux influence coefficient of other elements calculates by the same way.

Flux influence coefficient α _i,fmensuration

Select the daily comparison test sample of national cement Product Quality Verification Centers, cement type is the portland cement of PI type is tested sample, selects lithium tetraborate as flux, the bead of preparation 15 different dilution ratios.Adopt RIGAKUZSXPrimusIIX ray fluorescence analysis instrument (end window Rh target X-ray tube) to carry out x-ray fluorescence intensity mensuration to each bead, Instrument working parameter is in table 1, and measurement result is in table 2.

According to I and the RI data in table 2, and establish concentration of element C _ibe 100, initial point carried out to I and RI and does linear regression analysis and obtain K ₂and K ₁, the flux influence coefficient α of each element is namely obtained by above-mentioned formula (10) _i,f, the results are shown in Table 2.

Concentration C in table 2 _ivalue is all set as 100, also can with concentration value actual in sample.Adopt different C _ivalue, K in two slopes during regretional analysis ₂and K ₁have difference, but its ratio cc _i,fwith concentration value C _iit doesn't matter, only relevant with the ratio of slope, therefore any C _ivalue does not affect the mensuration to flux influence coefficient.

The measuring condition of each element of table 1

	Al	Ca	Fe	Mg	Si
						Voltage	50	50	50	50	50
Electric current	60	60	60	60	60
						Collimating apparatus	S4	S2	S3	S4	S4
Crystal	PET	LiF1	LiF1	RX25	PET
						Spectrum peak angle	144.79	113.1	57.504	38.38	109
Measuring Time	10	20	10	20	20
						PHA	100-300	100-300	100-300	100-300	100-300

Table 2 flux influence coefficient α _i,fask calculation result

Standard dilution is than the acquisition of lower x-ray fluorescence intensity

If obtain standard dilution than x-ray fluorescence intensity when being 5, then according to formula (13)

$I_0=I\&times;\frac{1+{\mathrm{R\&alpha;}}_{i,f}}{1+R_0{\mathrm{\&alpha;}}_{i,f}}---\left(13\right)$

Calculate, wherein R is actual dilution ratio, α _i,ffor the flux influence coefficient of element i, I ₀for standard dilution than under x-ray fluorescence intensity, R ₀standard dilution ratio, R herein ₀=5.

The x-ray fluorescence intensity result of element when some fuse piece sample is converted into standard dilution than 5 in table 2 is as shown in table 3.The relative deviation of each Main Ingredients and Appearance standard dilution specific strength calculating concentration is also list in table 3.Table 3 result shows, by the flux influence coefficient α of measuring _i,fthe standard dilution specific strength calculated, all can obtain stable result in the scope that dilution ratio is 4 to 10.

Table 3 obtains standard dilution than x-ray fluorescence intensity result when being 5

In order to investigate the calibration result of flux influence coefficient to different sample, the present invention adopts another cement sample (to be the daily comparative sample from national cement Product Quality Verification Centers equally, cement type is P.O Portland cement), prepare the serial print of different dilution ratio, fluorescence intensity measurement is carried out to it, then by flux influence coefficient, intensity correction is carried out to it, in table 4, as can be seen from the results, for the sample (R=3.75-10) of this serial different dilution ratio, this method is adopted all to can be exchanged into the intensity of standard dilution ratio (R=5).

Table 4 flux influence coefficient α _i,fto the correction result of different sample

In order to investigate the applicability of this method, embodiments of the invention are also provided in the measuring and calculating (instrument is PANalytical Axios and PhilipsPW2424) different luminoscopes carrying out flux influence coefficient, the results are shown in Table 5.

Table 5 different model instrument is to flux influence coefficient α _i,fask calculation result

INSTRUMENT MODEL	INT-SiO 2	INT-Fe 2O 3	INT-Al 2O 3	INT-CaO	INT-MgO
						PANalytical AXIOS	0.562	0.079	0.642	0.267	0.599
Philips PW2424	0.559	0.083	0.643	0.262	0.713

In order to investigate different flux influence coefficient to the calibration result of fluorescence intensity, the standard model of the present invention to some different dilution ratios carries out intensity correction (adopting the flux influence coefficient of PANalyticalAXIOS), and the intensity after correcting is adopted typical curve Computing Meta cellulose content, acquired results and standard results are all within the scope of permissible error (error range standard is with reference to GB/T176 Method for chemical analysis of cement), the results are shown in Table 6, table 7.

Table 6 different flux influence coefficient α _i,fto the correction result of fluorescence intensity

Intensity before correcting	SiO 2	Al 2O 3	Fe 2O 3	CaO	MgO	R
							JBW01-6-14 Portland cement	46.365	10.8961	52.6231	107.058	1.92443	5.359
GBW03201a portland cement	44.7023	10.698	66.9385	108.902	1.04289	5.404
							GSB08-1355-2008 grog	50.3489	10.5752	59.0289	119.348	1.50881	4.829
Intensity after correcting	SiO 2	Al 2O 3	Fe 2O 3	CaO	MgO
							JBW01-6-14 Portland cement	48.83491	11.49038	53.70263	111.3734	2.034969
GBW03201a portland cement	47.44604	11.36564	67.98781	113.9154	1.088549
							GSB08-1355-2008 grog	49.07134	10.30047	58.4521	117.0565	1.467529

The standard value of table 7 standard model and the measured value of this method

Standard value	SiO 2	Al 2O 3	Fe 2O 3	CaO	MgO
						JBW01-6-14 Portland cement	22.06	5.18	2.64	63.01	2.72
GBW03201a portland cement	21.26	5.19	3.30	64.48	1.47
						GSB08-1355-2008 grog	22.19	4.68	2.92	66.39	1.98
Measured value	SiO 2	Al 2O 3	Fe 2O 3	CaO	MgO
						JBW01-6-14 Portland cement	21.99	5.23	2.65	62.99	2.69
GBW03201a portland cement	21.37	5.17	3.36	64.41	1.44
						GSB08-1355-2008 grog	22.18	4.69	2.89	66.07	1.94

Said method provided by the invention, the x-ray fluorescence intensity of element to be measured in any dilution ratio fuse piece can be converted to the x-ray fluorescence intensity of element to be measured in certain specific dilution ratio fuse piece, and then can the disposal route of dilution ratio fuse piece of specific by this (fixing) any dilution ratio fuse piece be processed accordingly, complete the XRF analysis to element to be measured in fuse piece.

The above, it is only preferred embodiment of the present invention, not any pro forma restriction is done to the present invention, although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention, any those skilled in the art, do not departing within the scope of technical solution of the present invention, make a little change when the technology contents of above-mentioned announcement can be utilized or be modified to the Equivalent embodiments of equivalent variations, in every case be the content not departing from technical solution of the present invention, according to any simple modification that technical spirit of the present invention is done above embodiment, equivalent variations and modification, all still belong in the scope of technical solution of the present invention.

Claims (5)

1. obtain the method for standard dilution than lower x-ray fluorescence intensity, it is characterized in that comprising:

Step 1, is prepared as bead by tested sample, and the dilution ratio of this bead is R;

Step 2, carries out X-fluorescence strength detection to the bead of above-mentioned preparation, obtains the X-fluorescence intensity level I of certain element in sample;

Step 3, according to formula: calculate standard dilution and compare R ₀under X-fluorescence intensity I ₀, wherein α _i,ffor flux influence coefficient;

Described flux influence coefficient α _i,fobtained by following steps,

Step S1, with flux and the multiple bead of tested sample preparation, each bead has different dilution ratio R;

Step S2, carries out x-ray fluorescence intensity mensuration to above-mentioned each bead, obtains the x-ray fluorescence intensity I of certain element i in each bead;

Step S3, if the concentration of element i is Ci in above-mentioned tested sample, crosses initial point with the concentration C i of element i to I and RI and does multiple linear regressive analysis, obtains two slopes and is designated as slope K 1 and slope K 2, then flux influence coefficient α _i,f=K2/K1.

2. acquisition standard dilution according to claim 1 is than the method for lower x-ray fluorescence intensity, it is characterized in that: the dilution ratio R described in step 1 is within the scope of 3-10.

3. acquisition standard dilution according to claim 1 is than the method for lower x-ray fluorescence intensity, it is characterized in that, described tested sample is cement.

4. the measuring method of constituent content in cement sample, it is characterized in that, it comprises the method for the acquisition standard dilution described in any one of the claims 1-3 than lower x-ray fluorescence intensity, and by described X-fluorescence intensity I ₀with typical curve Computing Meta cellulose content after correcting.

5. the assay method of flux influence coefficient in x-ray fluorescence analysis, is characterized in that comprising the following steps:

Step S1, with flux and the multiple bead of tested sample preparation, each bead has different dilution ratio R;

Step S2, carries out x-ray fluorescence intensity mensuration to above-mentioned each bead, obtains the x-ray fluorescence intensity I of certain element i in each bead;

Step S3, if the concentration of element i is Ci in above-mentioned tested sample, crosses initial point with the concentration C i of element i to I and RI and does multiple linear regressive analysis, obtains two slopes and is designated as slope K 1 and slope K 2, then flux influence coefficient is by formula α _i,f=K2/K1 calculates.