CN101294895A - Transverse heating graphite furnace constant magnetic field Zeeman atomic absorption photometer for non-standard analysis - Google Patents

Abstract

A standard-less analysis used transverse heating graphite furnace constant magnetic filed Zeeman atomic absorption photometer is to be built. The patent of tungsten and tantalum graphite pipe provided by the inventor is used. The transverse heating of the graphite pipe is realized through a contact graphite bridge ring with the top and the bottom being 1mm wide, and a graphite cone ring is provided with an upper and a lower flat water-cooled jackets. Two 17.5*17.5*0.4mm pyrolytic graphite sheets are respectively attached on the front and the back of a permanent magnet and inserted in a lower graphite cone, with a clearance of 0.5mm being kept from an upper graphite cone, see the attached figure. The m exp values of 62 elements are listed on table 1; through linearization, integrated absorption Q obtains a Q used table 2, and formulae 5, 6 and 7. Standard solution in table 3 is used for accurately marking that k is equal to m exp/ m exp and mark A and Beta values. The elements to be detected use a fundamental formula 1.

Description

No standard analysis is with laterally heating the permanent magnetic field of graphite furnace Zeeman atomic absorption photometer

The present invention relates to not have standard analysis with laterally heating the permanent magnetic field rotation of graphite furnace (THGA) Rochon prism polarized light Zeeman deduction (Z, PM) atomic absorption spectrophotometer (AAS) (GFAAS).

W in 1993, Frech, B, V, L ' vov (Spectrochimica Acta ( 48B), 1371 (1993)) graphite furnace (THGA) of the horizontal heating of two end band caps (end cap) is proposed, be used in combination vertical alternating magnetic field Zeeman background deduction instrument PE company and produced PE4100ZL, 5100ZL, AAnalyst ^TM800 and the AAnalyst of multielement ^TM600 types.The two ends water-cooled graphite furnace (HGA type) of PE company production in 1970 still occupies each big manufacturer principal market, the world at present, its shortcoming be since two ends water-cooled element to be measured and matrix in two water-cooled end condensations, consequently 1. need to improve atomization temperature and just can overcome element steam to be measured condensation in cold junction, improving atomization temperature causes the graphite-pipe life-span to shorten, graphite-pipe heat radiation noise increases, baseline signal to noise ratio (S/N ratio) decline variation, detection limit descends.To high temperature element Os, B, Mo, V, Ti, U rare earth element etc. produce serious memory effect, even still can not eliminate in 20 seconds up to 3000 ℃ (3200K).2. the matrix condensation causes background absorption to strengthen in two water-cooled ends, when background absorption surpasses 2.0, promptly uses Zeeman deduction background also to be difficult to deduction.The matrix at condensation two ends increases matrix to be disturbed and matrix effect.Promptly use and put the highest general improver 1mg/ml Zr+0.5mg/ml Pd+10mg/ml tartrate of rate in 1%V/V HNO ₃Still be difficult to eliminate.Therefore be difficult to the direct mensuration of solid sample with the HGA graphite furnace.

After using end cap THGA, because whole graphite-pipe temperature is evenly constant during atomization, do not exist element to be measured and matrix condensation in two ends, the result is for 1. same element determination temperature is lower 200 to 300 ℃ than HGA at end cap THGA, the graphite-pipe life-span can extend to the low temperature element 1000～3000 times, in warm element 500～1000 times, high temperature element 200～500 times.Survey Mo, V, Ti only need 2500 ℃ (2700K) to get final product atomization in 8 seconds, and do not have memory effect.Atomization temperature descends also can reduce the heat radiation noise, improves signal to noise ratio (S/N ratio), reduces detection limit.2. reducing background absorption, is example with sample introduction 3 μ l seawater, and background absorption has surpassed the Zeeman deduction background allowed band greater than 2.0 when the HGA, but at end cap THGA only 0.3.Therefore use end cap THGA directly to measure complicated solid sample closely during the last ten years, used the aqueous suspension sampling system mostly.Need not the loaded down with trivial details molten sample step of working costs, also exempt HNO ₃, HCIO ₄, the blank high purification difficult shortcoming of HF acid, more time saving and energy saving.Therefore using the THGA graphite furnace is following graphite furnace analysis, especially for the main developing direction of no standard analysis.

The permanent magnetic field rotatory polarization Zeeman atomic absorption spectrophotometry luminosity that Hitachi, Ltd has patent can only be used for the HGA graphite furnace, and having model has 170-70,180-70, Z8000, Z5000 and Z5700 etc.The alternating magnetic field Zeeman atomic absorption photometer that has patent with PE company is compared, and need not to consume the extra nearly 5KW electric energy of alternating magnetic field that supplies when atomization, and it is to need not power consumption that permanent magnet is used in permanent magnetic field.The present inventor is using 170-70 of Hitachi and the work of Z8000 recent two decades to find; the HGA graphite body of heater of Hitachi's design is big; two end water collars are big; cause heating rate slow; it is bigger to analyze high temperature element difficulty; therefore use the best atomization temperature of Hitachi, Ltd's instrument to exceed 200～300 ℃ than PE company; there is not the graphite protective sleeve around adding graphite-pipe; burnt rapidly by air oxidation even consume a large amount of Ar gas (up to 31/ minute) graphite-pipe; add and use the atomization temperature height, even use the pyrolysis coating graphite-pipe life-span usually to have only 100～200 times.Higher atomization temperature causes graphite-pipe heat radiation noise to increase, baseline signal to noise ratio (S/N ratio) variation, and detection limit descends.This is the fatal shortcoming of Hitachi, Ltd's instrument.

Use Hitachi, Ltd's permanent magnetic field polarization plug scape to buckle background and also have additional difficulty in end cap THGA graphite-pipe; because of THGA graphite-pipe fire end just in time is a permanent magnet; be difficult to fire end and graphite cannula thereof, the water-cooled end, Ar gas shiled labyrinth like this is contained in the permanent magnet.Emphasis of the present invention has solved this to seem to be difficult to overcome difficulties.

Heat Jie's coating graphite-pipe that the present invention uses is the same with the HGA graphite furnace, i.e. internal diameter 5.9mm, and external diameter 8.1mm, hot Jie's graphite-pipe thickness of coating is 0.05mm.Length is reduced to the 18mm of THGA graphite furnace by the 28mm of HGA graphite furnace.Sample holes still is 1.5mm.Two ends are because of need not the water-cooled heating, and graphite-pipe two ends need not 45 ° of lead angles.Be that graphite-pipe directly is cut into 18mm long (Fig. 1).The patent No. of still using the present inventor to propose is the full classification number G01N21/31 of ZL96103203X international monopoly " fixed metal tungsten (or tantalum) platform-graphite tube (being called for short WTaPGT) and fixing means thereof." difference is that graphite-pipe length makes 18mm (Fig. 1 (a)) into by 28mm.End cap is hot Jie's graphite annular cap, ring internal diameter 3.5mm, and external diameter is enclosed within 8.1mm graphite-pipe two ends, hot Jie's graphite-pipe thickness 0.4mm.See Fig. 1.

3. graphite-pipe horizontal heating 1. realizes by the wide contact graphite of 1mm bridged ring by 2 half garden pillars China ink conical rings up and down, sees Fig. 2.Two dull and stereotyped water collars 6. about the graphite conical ring had.Be close to permanent magnet 8., 4. the hot Jie's graphite flake of each a slice of front and back is of a size of 17.5 * 17.5 * 0.4mm and is inserted in down the graphite awl.Keep the 0.5mm gap with last graphite awl.Last water collar leaves injection port 2. so that sample introduction.One deck teflon insulation layer is wrapped up in the permanent magnet tapering 5. 8., and the teflon insulation layer is all posted in last lower water jacket junction 5..7. last water collar two ends respectively have a quartz window, and lower water jacket central authorities have argon overcoat tracheae 10. the interior cover of argon tracheae respectively to be arranged 9. in two sides, stop argon gas when atomization.Upper water sleeve has big electric current brace (12) to be connected with strong current transformer with lower water jacket.Water collar respectively has water inlet pipe and water outlet pipe (11) up and down.Last lower water jacket is installed on engineering nylon slab (20mm the is thick) base (16).Last water collar is fixed on the base (16) with fixedly tightening spiral (14).Last water collar fixedly is being equipped with spring (15) on the spiral, and spring is adjusted automatically when guaranteeing when atomization high temperature that graphite-pipe expands, and guarantees that big current path contact is good simultaneously again.

When graphite-pipe was installed, the big electric current connecting line with water jacket took off earlier, took out and tightened spiral (14).Can take out upper water sleeve.Old graphite-pipe is blown in taking-up, loads onto new graphite-pipe.Upper water sleeve is installed upper water sleeve injection port and graphite-pipe sample holes with one heart with orientation tool.Again with water jacket by on fixing spiral (13), tighten spiral (14), installation graphite-pipe step is finished.

When not having standard analysis, " no standard analysis " (is called for short WTaPGT, GFAAS) method of Ti Chuing and step with fixed metal tungsten or tantalum platform graphite furnace atomic absorption photometer to the patent of invention of using the present inventor to propose.No standard analysis with fundamental formular (1) is;

m＝Q _A，0 m ₀exp ^*/0.0044k R _z，pm＝Q _A，0 m _zexp ^*/0.0044k (1)

M (pg) is an amount of element to be measured in the formula (1).m ₀Exp ^*Be best test feature amount, the m of THGA ₀Exp ^*In the table 1 of patent " WTaPGT, GFAAS ", list.R _{Z, pm}=m ₀Exp/m _zThe exp value is also listed in this table 1.m _zExp ^*M for .62 element of the best test feature amount (pg) of permanent magnetic field Zeeman atomic absorption photometer _zExp ^*List in table 1, this is the core data part that the present invention does not have standard analysis.

Q in the formula (1) _{A, 0}Be the Q that measures _AObtain through linearization process.This be because experiment record and detected element m (pg) relation be parabolic curved, only at Q _A0.1-0.2 following near linear, i.e. Q _A=Q _{A, 0}Therefore to make Q _ARange of application expands Q to _A=0.9A _r, A _rThe Q of correspondence when reversing for permanent magnetic field Earth Oxides by Zeeman GFAAS curve _AValue must will obtain Q through linearization process _{A, 0}Value.The present inventor derived formula (2) in 1978; α ^*=(10 ^A+0.01-1) ^-1(2).Work as Q _ARange of application is less than 0.9A _rThe time, with formula (3); α ^*=(10 ^A-1) ^-1(3).

B.V.et al; Spectrochimica Acta 51B (6) 609-618 (1996) introduces tortuosity factor β, proposition formula

$\left(4\right),Q_A=\mathrm{<figure-callout\; id="1"\; label="log"\; filenames="A20071009722200241.png,A20071009722200242.png"\; state="\{\{state\}\}">log</figure-callout>}\frac{1+{\mathrm{\&alpha;}}^{*}}{10-\frac{(1+{\mathrm{\&alpha;}}^{*})Q_{A,0}}{(1-\mathrm{\&beta;}{Q}_{A,0})+{\mathrm{\&alpha;}}^{*}}}---\left(4\right)$

(1+ α) is normalization coefficient, and purpose makes different α ^*Value is at Q _AValue obtains Q below 0.1-0.2 _A=Q _{A, 0}Directly with formula (3), (4) obtain Q through linearization _{A, 0}Be difficult and infeasible.Another emphasis of the present invention is to calculate each Q by formula (3) (4) _AAt different A _rValue (from 0.8-7.0 interval 0.1) different beta value (0.39 ,-0.27 ,-0.14,0.00,0.10,0.24,0.39 seven value) correspondence obtains Q _{A, 0}Value. list in table 2..A _rValue is gone into .Q by four houses 5 _AValue be 0.1 or 0.2. work as Q _A(x) be three figure place (Q _A＜1.000) or four figures (Q _A＞1.000), β (y) does not drop on seven β values for one digit number (β (y)＜0.10) or two figure places (β (y)＞0.10). and available formula (5) (6) (7) is calculated by interpolation method.

Q _A，0(x，β(L))＝Q _A，0(L，β(L))+(Q _A(x)-Q _A(L))/(Q _A(H)-Q _A(L))(Q _A，0(H，β(L))--Q _A，0(L，β(L))) (5)

Q _A，0(x，β(H))＝Q _A，0(L，β(H))+(Q _A(x)-Q _A(L))/(Q _A(H)-Q _A(L))(Q _A，0(H，β(H))--Q _A，0(L，β(H))) (6)

Q _{A, 0}(x, β (y))=Q _{A, 0}(x, β (L))+(β (y)-β (L))/(β (H)-β (L)) (Q _{A, 0}(x, β (H))-Q _{A, 0}(x, β (L))) L represent low value in (7) formula (5) (6) (7), and H represents the high value.

A _r, β value, the coefficient of deviation k=m in the formula (1) _zExp ^*/ m _zExp depends on instrument, the ultimate analysis line, and the element lamp type, lamp current etc., another emphasis of the present invention is accurately to demarcate A _r, β, k value. and use the standard solution of 62 individual element content of a cover, the content reliability will definitely guarantee. general improver, its composition are 1mg/mlZr+0.5mg/mlPd+10mg/mltartaric Acid+1%v/vHNO ₃. at the high essence of general improver empty value, should use permanent improver 5mg/ml Zr+4mg/mlIr+10mg/mltartaric acid+1%v/vHNO to a part instead ₃At 160 ℃ of 40s, 1300 ℃ of 20s, 2400 ℃ of 10s atomization. Cd at this moment, Zn, Cu, Mn, Pb, Ag, Na, K, element blank such as Mg have been removed, and graphite-pipe includes that permanent improver 250 μ gZr+200 μ gIr can directly add complex fluid or solid sample is measured. and table 3 is listed permanent magnetic field Earth Oxides by Zeeman GFAAS and is used concentration of standard solution (ng/ml). only list standard (1) number liquid concentration, when 10 μ l sample introductions, with the atomization temperature (K) of specifying demarcation usefulness, T (K)=T ℃+200, the Q of 3 correspondences of tabulating (1) number liquid _{A, 0}0.044 ± 10%. (2) numbers liquid are three times of (1) number liquid, corresponding Q _{A, 0}0.132 ± 10%. (3) numbers liquid are ten times of (1) number liquid, corresponding Q _{A, 0}0.440 ± 10%.

(4) number liquid is (1) number liquid thirtyfold, corresponding Q _{A, 0}1.32 ± 10%. (5) numbers liquid are 100 times of (1) number liquid, corresponding Q _{A, 0}4.40 ± 10%. (6) numbers liquid are 300 times of (1) number liquid, corresponding Q _{A, 0}=13.2 ± 10% (1) (2) number liquid is mainly used in measures the k value.(3) (4) (5) liquid is mainly used in and measures the β value.(5)

(6) number liquid is mainly used in and measures A _rValue.

Demarcated k, β, A _rAfter the value, it is just fairly simple directly to measure in complex fluid and the solid sample concentration of element C to be measured with no standard analytical process.(1) directly with complex fluid sample size V _In(μ l) or complicated solid sample sample size m _In(mg) inject graphite-pipe.(2) set atomization temperature and press T (K)=T ℃+200 for T ℃, utilize table 1 to check in m _zExp ^*Value.(3) use (1)-(6) number liquid of table 3 to demarcate k, β, A in advance _rValue.

(4) atomization records Q _AValue is obtained Q with table 2 and formula (5) (6) (7) through linearization process _{A, 0}

(5) try to achieve detected element m (pg) value with formula 1.(6) constituent content C presses formula (8) in the complex fluid;

C＝m/V _in(pg/μl，ng/ml，μg/l)(8)。The element resultant is by formula (9) in the complicated solid sample;

C＝m/m _in(pg/mg，ng/g，μg/kg)(9)。

Using present inventor's patent WTaPGT is basis of the present invention.Have only the WTaPGT of use could guarantee m ₀The exp value is constant, just might use no standard analytical process.Carbon generates carbonide in other twenties elements (comprising Sr, Ba, U, B and 15 rare earth element) energy and the graphite-pipe, produces matrix effect and memory effect, and it is difficult that analysis is produced.Will keep k=1.00 or near 1.00 in not having accurate the analysis, β is near 0.00, A _rThe Q of value _AValue is the bigger the better, and needs to use the non-ferrous metal patent Lowe of total institute type high strength commodity lamp.The Sullivan type commodity high-intensity lamp that the EDL of PE house journal lamp and Australian Photron company produce.Present inventor 1973 and second optical instrument factory, Beijing development commodity WFD-Y3 atomic absorption photometer use 1: 5 pulse power supply hollow cathode lamp of dutycycle power supply also can obtain and above-mentioned commodity high-intensity lamp same effect, and WFX1A, 1B are produced in northern afterwards two photoproduction, 1C, 1D, 1E, 1F, 1E2,1E3,1F2B2,110,120,130 types continue to use.

The permanent magnetic field of THGA of the present invention Earth Oxides by Zeeman GFAAS is compared with the THGA alternating magnetic field GFAAS (PE4100ZL, 5100ZL, A Analyst 800,600) that present PE has patent, and its advantage is for can save the 5kw electricity consumption when atomization.Have the permanent magnetic field Earth Oxides by Zeeman GFAAS (170-70 of Hitachi of patent HGA with Hitachi, 180-70, Z8000, Z5000 etc.) compare,, can reduce the atomization temperature of use owing to eliminated element steam to be measured in the condensation of water-cooled end, improve graphite-pipe and use the Shou life, reduce the thermal radiation noise, improve detection limit, eliminate the memory effect that occurs when measuring the high temperature element.Because having eliminated sample vapor is condensate in the water-cooled end, reduce background absorption interference and matrix and disturb, matrix effect, directly measuring complicated solid sample becomes possibility.Thereby avoid time-consuming, loaded down with trivial details, the molten sample step that reagent blank is big, analytical approach is easier, quick and precisely.Make each Tianwan businessman's product instrument not only as analytical instrument, also be available as the standard metering instrument.Also has the various standard model function of similar quantity simultaneously, as the standard tool for transmitting.In the inorganic analytical chemistry field is that great revolution breaks through.

(1) 62 element of table 1 and the m of wavelength (nm) under different temperatures T (K) _zExp ^*(pg) value

(2) 62 elements of table 1 and the m of wavelength (nm) under different temperatures T (K) _zExp ^*(pg) value

(3) 62 elements of table 1 and the m of wavelength (nm) under different temperatures T (K) _zExp ^*(pg) value

(4) 62 elements of table 1 and the m of wavelength (nm) under different temperatures T (K) _zExp ^*(pg) value

(5) 62 elements of table 1 and the m of wavelength (nm) under different temperatures T (K) _zExp ^*(pg) value

(6) 62 elements of table 1 and the m of wavelength (nm) under different temperatures T (K) _zExp ^*(pg) value

Table 2 3., from recording Q _AValue gets Q through linearization process _{A, 0}

Table 2 4., from recording Q _AValue gets Q through linearization process _{A, 0}

Table 2 5., from recording Q _AValue gets Q through linearization process _{A, 0}

Table 2 6., from recording Q _AValue gets Q through linearization process _{A, 0}

Table 3, the concentration of standard solution that permanent magnetic field Zeeman button background THGA graphite furnace uses

Element	Li	Na	K	Rb	Cs	Cu	Ag	Au	Be	Mg	Ca	Sr
													Wavelength (nm)	670.8	589.0	766.5	780.0	852.1	324.7	328.1	2437	234.8	285.2	422.7	460.7
Temperature (K)	2400	1900	1800	1800	1900	2200	1900	2200	2500	2300	2600	2600
													m zexp *(pg)	5.05	2.48	2.66	7.07	27.0	12.9	6.45	27.5	1.45	0.954	0.998	1.87
Mark one (ng/ml)	5.0	2.5	2.7	7.0	27.0	13.0	6.5	28	1.5	1.0	1.0	1.9
													Element	Ba	Zn	Cd	Hg	Al	Ga	In	Tl	Ge	Si	Sn	Pb
Wavelength (nm)	553.5	213.9	228.8	253.7	309.2	287.4	303.9	276.7	265.2	251.6	286.3	283.3
													Temperature (K)	260	1900	1600	1300	2500	2500	2200	1900	2600	2600	2400	1900
m zexp *(pg)	8.17	1.006	1.081	191	24.0	40.8	26.8	46.3	60.1	45.7	51.5	22.7
													Mark one (ng/ml)	8.0	1.0	1.1	190	24.0	40	27	46	60	46	50	23
Element	As	Sb	Bi	Bi	Se	Te	Cr	Cr	Mn	Fe	Co	Ni
													Wavelength (nm)	193.7	217.6	223.1	306.8	196.0	214.3	357.9	359.3	279.5	248.3	240.7	232.0
Temperature (K)	2400	2400	2000	2000	2200	2200	2500	2500	2300	2500	2500	2600
													m zexp *(pg)	39.6	56.5	58.9	347	51.2	68.8	8.66	6.25	7.57	11.4	11.3	17.9
Mark one (ng/ml)	40	27	60	35	51	70	9.0	6.0	7.6	11.0	11.0	18.0
													Element	Pd	Pt	Rh	Ru	Sc	Y	Eu	Dy	Ho	Er	Tm	Yb
Wavelength (nm)	247.6	265.9	343.5	349.9	391.2	410.2	459.4	421.2	410.4	400.8	371.8	398.8
													Temperature (K)	2500	2600	2600	2600	2700	2700	2600	2700	2700	2700	2600	2500
m zexp *(pg)	35.8	180	40.0	90.0	20.3	121	24.3	49.4	39.9	43.3	9.4	3.06
													Mark one (ng/ml)	36	180	40	90	20	120	24	50	40	43	9.0	3.0
Element	P	Os	B	La	Ce	Pr	Nd	Sm	Gd	Tb	Lu	U
													Wavelength (nm)	213.6	290.9	249.8	550.1	463.2	495.1	463.4	429.7	407.9	432.6	336.0	358.5
Temperature (K)	2600	3100	2700	2700	2700	2700	2700	2700	2700	2700	2700	2700
													m zexp *(ng)	12.3	1.82	0.333	1.61	42.3	1.83	0.963	0.335	3.23	0.370	0.568	5.51
Mark one (μ g/ml)	12.0	1.8	0.33	1.6	42	1.8	1.0	0.33	3.2	0.37	0.57	5.5
													Element	Ir	Ti	V	Mo
Wavelength (nm)	265.0	365.4	318.5	313.3
													Temperature (K)	2600	2700	2700	2700
m zexp *(pg)	141	70.0	52.3	28.6
													Mark one (ng/ml)	140	70	52	30

Description of drawings

1; Fig. 1 is end cap WTaPGT and semicolumn graphite platform synoptic diagram; (1) injection port.(2) graphite-pipe.

(3)end cap。(4) tantalum piece among the WTaPGT.(5) tungsten filament.(4) semicolumn graphite platform in figure below.

2; Fig. 2 and Figure of abstract are THGA graphite furnace body structure (X-Z cross section) synoptic diagram; (1) graphite-pipe.

(2) injection port.(3) graphite awl bridged ring.(4) pyrolytic graphite sheet.(5) insulation course.(6) water collar.

(7) quartz window.(8) magnet.(9) interior tunger tube.(10) outer tunger tube.(11) water pipe.

(12) base plate.(13) fixed screw.(14) tighten the screws cap.(15) spring.(160 big electric current plates.

3; Fig. 3 is THGA graphite furnace body structure (X-Y cross section) synoptic diagram; (1) graphite-pipe.(2) injection port.

(3) graphite awl bridged ring.(4) pyrolytic graphite sheet.(5) insulation course.(6) water collar.(7) quartz window.

(8) magnet.(11) water pipe.

4; Fig. 4 is THGA graphite furnace body structure (Y-Z cross section) synoptic diagram; (1) graphite-pipe.(2) injection port.

(4) pyrolytic graphite sheet.(5) insulation course.(6) water collar.(8) magnet.(9) interior tunger tube.

Claims (5)

1。The present invention relates to not have standard analysis with laterally heating the permanent magnetic field rotation of graphite furnace Rochon prism polarized light Zeeman background deduction atomic absorption photometer.Use two ends band caps (end cap) pyrolysis coating graphite-pipe, long 18 millimeters, 8.1 millimeters of external diameters, 5.9 millimeters of internal diameters, 0.05 millimeter of pyrolysis coating.Patent ZL96103243X with present inventor's proposition, " " end cap is the strong cap of pyrolytic graphite ring to the full classification number G01N21/31 of international monopoly for fixed metal tungsten or tantalum platform-graphite tube and fixing means thereof, 3.5 millimeters of ring internal diameters, external diameter is enclosed within 8.1 millimeters graphite-pipe two ends, 0.4 millimeter of pyrolysis thickness of coating.Survey Mo, V, Ti, Pd, Pt, Ru, Rh, Ir, 5.8 millimeters of external diameters of Os, long 18 millimeters, thick 0.4 millimeter full coating graphite tube is sawn into two semicircular ring as platform, sees Fig. 1.The horizontal heating of graphite-pipe (1) is touched graphite-pipe (3) by two halves cylinder graphite conical ring up and down by 1 mm wide graphite annulus bridge knot, sees Fig. 2.Graphite conical ring (3) cooling two dull and stereotyped water collars (6) up and down.Nearly each a slice pyrolytic graphite sheet 17.5x17.5x0.4 millimeter (4) of permanent magnet awl (8) front and back that pastes is inserted in down the graphite awl, keeps 0.5 millimeter gap with last graphite awl.Last water collar leaves injection port (2)., over against the graphite-pipe injection port.A layer insulating (5) is wrapped up in the magnet tapering, and insulation course (5) is all posted in last lower water jacket contact position.Respectively there is a quartz window (7) at last water collar two ends.There is outer argon cover tracheae (10) in following water collar central authorities, respectively there is an interior tunger tube (9) both sides, stop the supple of gas or steam during atomization again. upper water sleeve and lower water jacket respectively have a big electric current plate (12) and strong current transformer to connect. going up lower water jacket respectively has water inlet pipe and water outlet pipe (11). go up lower water jacket and be installed on thick 20 millimeters nylon sheet bases (16). upper water sleeve is fixed on the base plate (16) with fixed screw (13) and tighten the screws cap (14). upward on the fixed screw of water collar by spring (15) is arranged, guarantee that spring is adjusted automatically when atomization pyrographite tube swelling, guarantee that simultaneously big current path contact is good.

When graphite-pipe is installed, big electric current tie with upper water sleeve takes off earlier, takes out tighten the screws cap (14) and screw (13), can take out upper water sleeve and old graphite-pipe, load onto new graphite-pipe. when pressing upper water sleeve, upper water sleeve injection port and graphite-pipe sample holes are pressed dress with one heart with orientation tool.Upper water sleeve is fixed on the base (16) with fixed screw (13) and tighten the screws cap (14).See Fig. 2.

When not having standard analysis, " no standard analysis " (is called for short WTaPGT, GFAAS) method of Ti Chuing and step with fixed metal tungsten or tantalum platform graphite furnace atomic absorption photometer to the patent of invention of using the present inventor to propose.No standard analysis with fundamental formular (1) is;

m＝Q _A，0m ₀exp ^*/0.0044k R _z，pm＝Q _A，0m _zexp ^*/0.0044k (1)

M (pg) is an amount of element to be measured in the formula (1).m ₀Exp ^*Be best test feature amount, the m of THGA ₀Exp ^*In the table 1 of patent " WTaPGT, GFAAS ", list.R _{Z, pm}=m ₀Exp/m _zThe exp value is also listed in this table 1.m _zExp ^*M for .62 element of the best test feature amount (pg) of permanent magnetic field Zeeman atomic absorption photometer _zExp ^*List in table 1, this is the core data part that the present invention does not have standard analysis.

Q in the formula (1) _{A, 0}Be the Q that measures _AObtain through linearization process.This is because the Q that experiment records _AAnd detected element m (pg) relation is parabolic curved, only at Q _A0.1-0.2 following near linear, i.e. Q _A=Q _{A, 0}Therefore to make Q _ARange of application expands Q to _A=0.9A _r, A _rThe Q of correspondence when reversing for permanent magnetic field Earth Oxides by Zeeman GFAAS curve _AValue must will obtain Q through linearization process _{A, 0}Value.The present inventor derived formula (2) in 1978; α ^*=(10 ^A+0.01-1) ^-1(2).Work as Q _ARange of application is less than 0.9A _rThe time, with formula (3); α ^*=(10 ^A-1) ^-1(3).

B.V.et al; Spectrochimica Acta 51B (6) 609-618 (1996) introduces tortuosity factor β, proposition formula

$\left(4\right),Q_A=\log \frac{1+{\mathrm{\&alpha;}}^{*}}{10-\frac{(1+{\mathrm{\&alpha;}}^{*})Q_{A,0}}{(1-\mathrm{\&beta;}{Q}_{A,0})+{\mathrm{\&alpha;}}^{*}}}---\left(4\right)$

(1+ α) is normalization coefficient, and purpose makes different α ^*Value is at Q _AValue obtains Q below 0.1-0.2 _A=Q _{A, 0}Directly with formula (3), (4) obtain Q through linearization _{A, 0}Be difficult and infeasible.Another emphasis of the present invention is to calculate each Q by formula (3) (4) _AAt different A _rValue (from 0.8-7.0 interval 0.1) different beta value (0.39 ,-0.27 ,-0.14,0.00,0.10,0.24,0.39 seven value) correspondence obtains Q _A.0Value.

List in table 2..A _rValue is gone into .Q by four houses 5 _AValue be 0.1 or 0.2. work as Q _A(x) be three figure place (Q _A＜1.000) or four figures (Q _A＞1.000), β (y) does not drop on seven β values for one digit number (β (y)＜0.10) or two figure places (β (y)＞0.10). and available formula (5) (6) (7) is calculated by interpolation method

Q _A.0(x，β(L))＝Q _A，0(L，β(L))+(Q _A(x)-Q _A(L))/(Q _A(H)-Q _A(L))(Q _A，0(H，β(L))--Q _A，0(L，β(L)))(5)

Q _A，0(x，β(H))＝Q _A，0(L，β(H))+(Q _A(x)-Q _A(L))/(Q _A(H)-Q _A(L))(Q _A，0(H，β(H))--Q _A，0(L，β(H)))(6)

Q _A，0(x，β(y))＝Q _A，0(x，β(L))+(β(y)-β(L))/(β(H)-β(L))(Q _A，0(x，β(H))-Q _A，0(x，β(L)))(7)

In the formula (5) (6) (7) Represent low value, H represents high value.

A _r, β value, the coefficient of deviation k=m in the formula (1) _zExp ^*/ mz exp depends on instrument, the ultimate analysis line, and the element lamp type, lamp current etc., another emphasis of the present invention is accurately to demarcate A _r, β, k value. and use the standard solution of 62 individual element content of a cover, the content reliability will definitely guarantee. general improver, its composition are 1mg/mlZr+0.5mg/mlPd+10mg/mltartaric Acid+1%v/vHNO ₃. at the high essence of general improver empty value, should use permanent improver 5mg/ml Zr+4mg/mlIr+10mg/mltartaric acid+1%v/vHNO to a part instead ₃At 160 ° of C40s, 1300 ° of C20s, 2400 ° of C10s atomization. Cd at this moment, Zn, Cu, Mn, Pb, Ag, Na, K, element blank such as Mg have been removed, and graphite-pipe includes that permanent improver 250 μ gZr+200 μ gIr can directly add complex fluid or solid sample is measured. and table 3 is listed permanent magnetic field Earth Oxides by Zeeman GFAAS and is used concentration of standard solution (ng/ml). only list standard (1) number liquid concentration, when 10 μ l sample introductions, with the atomization temperature (K) of specifying demarcation usefulness, T (K)=T ° C+200, the Q of 3 correspondences of tabulating (1) number liquid _{A, 0}0.044 ± 10%. (2) numbers liquid are three times of (1) number liquid, corresponding Q _{A, 0}0.132 ± 10%. (3) numbers liquid are ten times of (1) number liquid, corresponding Q _{A, 0}0.440 ± 10%. (4) numbers liquid are (1) number liquid thirtyfold, corresponding Q _{A, 0}1.32 ± 10%. (5) numbers liquid are 100 times of (1) number liquid, corresponding Q _{A, 0}4.40 ± 10%. (6) numbers liquid are 300 times of (1) number liquid, corresponding Q _{A, 0}=13.2 ± 10%. (1) (2) numbers liquid are mainly used in measures the k value.(3) (4) (5) liquid is mainly used in and measures the β value.(5) (6) number liquid is mainly used in and measures A _rValue.

Demarcated k, β, A _rAfter the value, it is just fairly simple directly to measure in complex fluid and the solid sample concentration of element C to be measured with no standard analytical process.(1) directly with complex fluid sample size V _In(μ l) or complicated solid sample sample size m _In(mg) inject graphite-pipe.(2) set T ° of C of atomization temperature and press T (K)=T ° C+200, utilize table 1 to check in m _zExp ^*Value.(3) use (1)-(6) number liquid of table 3 to demarcate k, β, A in advance _rValue.

Check in m _zExp ^*Value.(3) use (1)-(6) number liquid of table 3 to demarcate k, β, A in advance _rValue.

(4) atomization records Q _AValue is obtained Q with table 2 and formula (5) (6) (7) through linearization process _{A, 0}

(5) try to achieve detected element m (pg) value with formula 1.(6) constituent content C presses formula (8) in the complex fluid;

C＝m/V _in(pg/μl，ng/ml，μg/l)(8)。Constituent content is by formula (9) in the complicated solid sample;

C＝m/m _in(pg/mg，ng/g，μg/kg)(9)。

2。Described by claim 1;

62 elements are at the m of the permanent magnetic field of ehd cap THGA Earth Oxides by Zeeman GFAAS at different atomization temperature T (K) _zExp ^*Value is listed in table 1.

3。Described by claim 1;

Using present inventor's patent WTaPGT is basis of the present invention.Have only the WTaPGT of use could guarantee m ₀The exp value is constant, just might use no standard analytical process.Carbon generates carbonide in other twenties elements (comprising Sr, Ba, U, B and 15 rare earth element) energy and the graphite-pipe, produces matrix effect and memory effect, and it is difficult that analysis is produced.

4。Described by claim 1;

Will keep k=1.00 or near 1.00 in not having accurate the analysis, β is near 0.00 .A _rThe Q of value _AValue is the bigger the better, and needs to use the non-ferrous metal patent Lowe of total institute type high strength commodity lamp.The Sullivan type commodity high-intensity lamp that the EDL of PE house journal lamp and Australian Photron company produce.Present inventor 1973 and second optical instrument factory, Beijing development commodity WFD-Y3 atomic absorption photometer use 1: 5 pulse power supply hollow cathode lamp of dutycycle power supply also can obtain and above-mentioned commodity high-intensity lamp same effect, and WFX1A, 1B are produced in northern afterwards two photoproduction, 1C, 1D, 1E, 1F, 1E2,1E3,1F2B2,110,120,130 types continue to use.

5。Described by claim 1;

The permanent magnetic field of THGA of the present invention Earth Oxides by Zeeman GFAAS is compared with the THGA alternating magnetic field GFAAS (PE4100ZL, 5100ZL, A Analyst 800,900) that present PE has patent, and its advantage is for can save the 5kw electricity consumption when atomization.Have the permanent magnetic field Earth Oxides by Zeeman GFAAS (170-70 of Hitachi of patent H G A with Hitachi, 180-70, Z8000, Z5000 etc.) mutually this owing to eliminated element steam to be measured, can reduce the atomization temperature of use in the condensation of water-cooled end, improve graphite-pipe and use the Shou life, reduce the thermal radiation noise, improve detection limit, eliminate the memory effect that occurs when measuring the high temperature element.Because having eliminated sample vapor is condensate in the water-cooled end, reduce background absorption interference and matrix and disturb, matrix effect, directly measuring complicated solid sample becomes possibility.Thereby avoid time-consuming, loaded down with trivial details, the molten sample step that reagent blank is big, analytical approach is easier, quick and precisely.Make each Tianwan businessman's product instrument not only as analytical instrument, also be available as the standard metering instrument.Also has the various standard model function of similar quantity simultaneously, as the standard tool for transmitting.In the inorganic analytical chemistry field is that great revolution breaks through.

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