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Spectrochimiea

Actn, 1954,Yol.6,pp. 198 to 210. Pergamon PressLtd., London

The spectrochemical determination of impurities in copper and copper alloys by means of a spark-ignited arc-like discharge
FREDERICK V. SCHATZ
Research Department, Revere Copper and Brass, Inc., Rome, New York (Receivecl13 November 1953)

Summary-A spectrochemical method of analysis of copper and copper alloys with a sensitivity capable of detecting lead, tin, iron, nickel, silicon, bismuth and aluminium at O.OOl%, tellurium, arsenic and phosphorus at 0.004’7& and zinc at 0.01% is described. This method differs from the conventional arc analysis in that it is based on the excitation in a selected region in the vicinity of the cathode when using a special triggered discharge of the Multisource. If the circuit constants of the Multisource are adjusted to give a heavily, over-damped discharge, and if the sample is made negative, a narrow region of enhanced sensitivity exists for certain elements in the vicinity of the cathode. This region has been demonstrated to be equivalent to the cathode layer in D.C. arc. Variations in the relative sensitivities of certain elements, as well as variations in the excitation temperature, have been investigated for various points across the discharge gap.

1. Introduction
Recent trends in spectrochemical analysis, especially on the part of the large metal producing industries, have been toward fast automatic methods of analysis, utilizing the direct-reading spectrometer. This trend has introduced problems which, though not serious in a spectrographic laboratory where non-routine analyses predominate, have become increasingly important to the dire$ reading analyst. Most of these problems centre around simplifying and standardizing analysis procedures, and at the same time increasing precision and sensitivity. Applied specifically to the copper and brass industry, the problem involves combining into a simplified procedure a method of high precision, capable of determining 40% zinc with an error of 1% of content or less, and a method of extreme sensitivity, capable of determining impurity elements present in amounts of O.OOlo/o or lower. In a previous paper [l] the author described a procedure which handled the above problem with considerable success. Briefly, this procedure utilized several point-to-plane discharges, with a flat cast-metal specimen as the plane and a graphite electrode as the point. Different discharge characteristics were obtained by adjusting the capacity, inducta.nce and resistance in the power circuit of the Applied Research Laboratories Multisource [a]. By means of these spark igriited discharges, 30% zinc in 70-30 brass was analyzed with an error of &0.35% of content, and impurity elements were detected down to concentrations of 0.01-0.02 in yellow brass and 0.02-0.05°/0 in red brass and copper. This original work was repeated by others [3] and has provided the basis for a successful direct-reading method of analysis. Although these sensitivities were adequate for the analytical control of a large number of alloys, an equally large number of high purity alloys and refined copper remained to be analyzed by other methods. 19%

iron. The procedures. One lens with its axis horizont’al was placed at the spectrograph slit to focus t’he image of the discharge vert. all detected at 0. nickel. t. tellerium. The components of the arrangement. In addition to disrupting working schedules. horizontal adjust’ment of the discharge position will enable the system to analyze 10 p sections across t’he discharge from the sample plane to the counter electrode. and zinc.C.he met’hod has the same simplicity and speed of operation as the conventional analyses using solid samples and point-to-plane sparking techniques. arsenic and phosphorus. oxides.iply the basic analysis cost per sample by large and unpredictable factors. bismuth and aluminium.C.u in width. defining a discharge cross-sect’ion 10 .01%.C.004$1/. Also once inst’alled and adjusted.ically on t’he collimator opening wit’h a magnification of 6. A horizontal arrangement of the conventional Petrey stand was devised to 199 . The optical arrangement for isolating t’he lamellae along the length of the discharge employed two crossed cylindrical condensing lens combined in a manner suggested by HANSEN [4]. In the present instance a 40 p slit was used. arc type of analysis. detected at 0. each lamella emitting radiation characteristics of the stat’e of affairs wit’hin its small volume. use self-electrodes.001%. The resolution of the system. and is based on an unusual experimental arrangement. arc-like discharge of high sensitivity.0. If the axis of the spark discharge is made horizontal. The excitation source was an Applied Research Laboratories Multisource [2]. t’hough not new. The sensitivity of detection of phosphorus in copper. Experimental arrangement The method in its ult’imate form was a natural outgrowth from an invest’igat’ion of t’he distribution of certain element line int’ensities across the discharge. however. arc excitation in general are very good. based principally on D. is better than any previous met’hod investigated by the author. solut’ions. arc excitat. t’hey mult. or metal globules. for example. The second lens wit’h its axis vertical was placed in front of the discharge to focus t’he image of the discharge horizont’ally on t’he slit with a magnification of 4. tin. The spectrograph was a large Bausch and Lomb Littrow model using quartz optics. silicon. detected at 0. Elements investigated in detail were lead. do yield unique results when combined in the experiment to be described. are often very unsatisfactory or even impossible when viewed from the standpoint of fast analytical control. 2. Results based on D.The spectrochemical determination of impurities in copper and copper alloys These other methods. t. the discharge was considered to be composed of a set of lamellae parallel to the sample plane.e.5. In order to examine line intensities emanating from the vapour cloud at various dist’ances from the sample. the thickness of the lamella. The electrode system was a conventional point-to-plane type consist’ing of a machined metal surface and a pointed graphite counter electrode.. Consequently. is defined by t’he slit width.he radiation received by the system will be from the lamellar volume described above. Applied to copper alloys it has an inherent relative sensitivity for some elements equal to all but the most refined D. The method described in this paper utilizes a spark-ignited.ion. i. This situat’ion is aggravat’ed to the extreme when direct-reading spectrometers are used.

easily machinable.. The whole assembly was then mount. Investigation of intensity variations of selected elements across the discharge gap Three types of discharges commonly used in copper alloy analysis were studied for line intensity variations across the discharge gap (see Table 1). The posit’ion of the discharge gap with respect to the optic axis can be maintained if fiducial marks and an appropriate scale are placed on the auxiliary screen once the init. This cathode enhancement increased from a small value in the slightly underclamped discharge to a very pronounced effect in the heavily overdamped discharge. In the heavily overdamped or Type 2 discharge line int’ensit.ies of certain element..FREDERICK V. 3. Initial adjustment’s of the optical system were made with a line-filament microphotometer lamp placed wit’h t. an auxiliary lens was placed on the optic axis at the rear of the system and an enlarged image of the count’er electrode was projected on a screen. ’ Precision I ’ I Sensitizdy Typical setting I 2.. To facilitate horizontal adjustment and to furnish convenient reference point)s. 200 /‘H.* 10 Cl 60 /IF. Heavily overdamped 3. With the sample posit. it was selected for study.uH distributed inductance. j Sample Types of discharge polarity ~ .* 20 R 10 /LF. The horizontal and vertical images were then centred at the slit and the collimator respectively..s were found to be greatly enhanced in a narrow region close to the negative 200 . The spark stand was split horizontally for this purpose. As the heavily overdamped discharge had the most pronounced effect in combination with a 20 to 1 increase in overall sensitivity.ive none of the discharges showed any unusual variation in line intensities Table 1. asbestos board. in the region adjacent to t’he sample electrode. Exact placement of the discharge gap was accomplished by aligning the image of the counter electrode after the position of its point with reference to the sample plane had been accurately set by means of a 2. 200 /‘H. Slightly underdamped / i + + * Settings include 25 .ransite.uF.5 mm gap spacer. an enhancement of line intensities appeared in the region adjacent to the cathode. To prevent the projecting surface of the sample from partially blocking the horizontally divergent rays..* 3 fl 1. The vertical adjustment was relatively coarse. The stand and electrode holder were mounted on a piece of t..he filament vertical at the location of the spark gap. with the sample negative.0% Error Poor Excellent Good 10 ..ed on the optical bench in a stand with a fine screw thread for accurate horizontal adjustment. SCHATZ facilitate the handling of flat samples (see Fig. 400 . However. placed in the position of t’he analysis sample.ial alignment is accomplished.uH. 1). Slightly overdamped 2. the vertical plane of the sample was placed at an angle of 54’ to a vertical plane along the optic axis.0% Error 10 O/cError 2. a hard.

rode in a 2. provided sufficient sample is excited to produce background. The result is a very reproducible arc spectrum in which t. are tellurium.ensities also tended to content was increased. this pulse length is about the maximum permissible with 60 cycle initiat. initiated and reached its maximum extent within approximately t)he first ten seconds of excit.o 15 to 1 in the case of lead.3 milliseconds.5 mm from the sample elect. was spread out in the verGea direction.ional. changing from 4. arc.3 millisecond interval between charging cycles.he brasses.ion where the line merges into background. Selected brass and copper samples containing various elements in small amounts were excited. Elements behaving like lead.e.o lead in t. i. Since discharge conditions reassert themselves each cycle with the condenser voltage returning to its peak value of 940 volts each time. As t.elat.here is an 8.ion. and spectra were photographed from sections of the diseharge 0. I-0. due to copper emission. Type 2 excitation can be considered an interr~lpted D.s cathode enhancement. from I to 1 to 6 to 1 in t.5. Visually. arc.sample electrode.at.5 mm discharge gap. heavily o~Ter~la~~ped pulses. time required for t. Tin is similar t.C. This e~haneement varies to some extent. 0. R.or control.ed and plotted on a logarit’hmic scale.he case of iron.o the are at each cycle by the ~ultisouree.he sample increases. 0.hat it. to obtain a comparative picture of the change in relative sensitivity of impurity element. It also may be considered proportional to the effective line-to-background ratio when background is present.5 to 1 t. and the line intensit&y is corrected for background intensity. Consequentsly. of t’he matrix. in that there is a pronounced cathode enhancement regardless of t’he zine cont’ent. Type 2 excitation is a series of ~~nidirect.he current to drop t’o 10% of its maximum value. when using a copper sample and t<ended to spread across the discharge as the zinc The region of enhanced line int. broaden with increased zinc content but not t’o as great an extent as the visual This glow appeared short’ly after the discharge was appearance would indicate. effective line-to-background intensity ratios were comput. with the line select~ed.hode enhancement in copper in comparison to that.C. This glow was at its narrowest. lines as the dist. the average arc voltage drop remains higher than in the continuous D. These results for a sensitive iron and lead line in both a 70-30 matrix and a copper matrix are shown in Fig. tin and bismuth. Computation shows each pulse to have a peak current of 45 amperes and a duration of 6. where the input mains remain connected to the circuit and current is limit. unlike interrupted arcs of the Pfeilsticker variety. l-5 and 2. This is evident from the large number of ion lines in addition to the usual atom lines. nickel.ance from t. Also.ive sensitivity is defined as the concentrat. The image of Ohis region was easily discerned since it.ransit. the image of t’he discharge at the slit’ also presented an unusual appearance in that in this same narrow region there was a pronounced greenish glow. is greatly increased 201 .ed only by the arc and a series ballast an accurately measured packet of charge is delivered t.25. Inspection of t’he curves shows an increase in cathode enhancement wit)h increasing copper content. but in the ease of low impurity elements the number of lines available for examination is usually restricted to the most sensitive arc lines. 2. Basically. Tellurium and nickel have a slightly redueed cat.ions from high energy levels are encouraged. in t.

copper demonstrated 6. In his papers. In a D. 6. The principles applying to copper are valid in general for it. 3 the intensity ratios of a few copper atom and ion lines are plotted as atom-atom and atom-ion combinations versus distance across the gap to demonstrate the variation in cathode enhancement for different lines of the same element. in copper. the reaction copper occurring at the cathode.0 mm - I. Oxygen copper arc the negative electrode is consumed while the anode with is necessary for the maintenance of the arc.5 I.y of the following points: Cu2634. 3. the cathode layer disappears and the line enhancement spreads across the arc gap. Bismuth was checked only in brasses where its cathode enhancement is very pronounced.s alloys.C.5 0. is untouched. 2. in that cat)hode enhancement’ becomes very slight when zinc content increases.0 arc. 202 .C. The above D. Variation in intensity ratios of selected copper line pairs amoss discharge gap.0 25 mm DISTANCE ACROSS DISCHARGE CAP- Fig. 4. vapour concentration in the arc rises. are arsenic and antimony.0 I.0 2. 2.91 / / 04 0 0. In Fig. MILBOURN qualitatively the validit.21 0 05 I. Fig. Variation in relative sensitivity of lead and iron mross t. 1. Aluminium showed Wle or no cathode enllancement in either 70-30 brass or copper. 5.he discharge gap.5 2.5 2. behaving like iron. Phosphorus and zinc have a pronounced cathode enhancement in copper.ween Type 2 discharge and the by MILBOURN [5] [S]. When the size of the sample at the cathode is reduced to a small globule. 3.FREDERICK SCHATZ V. Impurity lines behave generally like copper lines in that their arc radiations are strongest near the cathode and diminish in intensity across the arc. Ion-line radiations are emitted only near to the electrodes. as described material suggests a similarity bet. Elements.

Fig. . 1. View of spark stand and sample.

showing pin samples. Horizontal D.Fig. 4. .C. arc.

endency of a D. An 85-15 brass alloy containing 0.The spectrochemical determination of impurities in copper and copper alloys In order to make a direct comparison bet’ween the two kinds of discharge. The gap distance was adjusted to 2. However. t. This suggests the use of cathode layer in the above described D. diameter pin samples with hemispherical tips were found to be adequate for the purpose of comparison. equivalent to the average current. was used. but t’o a decrease in background which became quit’e low and erratic in the region of the anode. &-in.C. in the Type 2 discharge. due to the t.C. arc shows a relat’ive sensitivity approximately ten times greater than the corresponding layer in the Type 2 discharge.he cathode layer is present in both discharges and in the D.5 mm and a 3.C’. Some experimental difficulties were encountered. mm Fig. 4).hode.5 ampere arc current. Comparison of the relative sensitivities of Pb 1833 across the discharge in Type f and the D.C. in that the arc wandering could be kept reasonably within bounds in the opt’ical system and still not hang at one point’ (see Fig. and a series of spectra at varying distances from the cathode was made. arc. 5. In the Type 2 discharge.C. As indicated in t’he figure. where t’hey are superimposed for the sake of comparison.he detection of impurities at extremely high sensitivities. The increase in relative sensitivity at the anode in each case is not due t#o an increase in the effective intensity of the lead line. arc excitation for t. arc to eit’her hang on a point or t’o wander errat’ically. arc was devised.016% lead was used for bot#h anode and cat. using both types of excitation. 5. a horizontal D. the standard deviation for the intensity ratio Pb 2833/Cu 3030 was 203 . The variation in relative sensitivity of the Pb 28338 line versus distance across the gap is shown for both cases in Fig.

and in the cathode enhancement of the lead line. were determined at various locations across the discharge gap. Proceeding from the cathode to the anode.v.ive intensibies of these tin line pairs 204 .90 A flat copper sample containing approximately 0. arc.C.2% tin was excit. in the electrode attack.3.v.G. If t#emperature is the only parameter.5”. arc and 5. using a graphite counter electrode. e . indicate that Type 2 excitation is close to that of a D. The similarities in the spectra. we have for three tin line pairs: Sn 3262 . where I = measured intensity A = transition probabilit*y G = statistical v = frequency E = energy of init. Investigation of excitation temperature across the discharge gap The variation in the arc-spark line pair in Fig. the reduction in effective intensity of the lead line is approximately 10 to 1 in the case of the D.X0. The relative intensities of the same tin line pairs were also determined in t. 3 raises the question of whether the discharge is in thermal equilibrium at all points across the gap.C.G. arc.&) A.06 e Sn 3034 Sn 2850 _ ??$?!? --__ = 0.ed. at the cathode to 157” and greater at the anode.ial transition K = Boltzmann constant level weight T = absolute temperature L_~KGSTROTH and MCRAE [7] have determined the transition probabilities of selected tin lines in the course of an investigation of temperat’ures existing in a D. and that the cat’hode layers are similar in both types of discharge. The t#emperature computed from t’he relat. the relat’ive intensity of lines 1 and 2 is given by . and relative intensities of the above tin line pairs.C. which in both cases are strongly enhanced at the Type 2 discharge. spark and the D. corrected for background.he horizontal D.C. and ranged from approximately 107.C. 4.C. and A. cathode. Using values determined by them. standard deviations were not computed but appeared to be somewhat larger. extended across the Type 2 discharge. Also in both cases t’he cathode was consumed and the anode was relatively untouched.5 to 1 in the case of the Ion lines. In the D. arc. arc using pin samples of the dimensions described before./ in the centre of the discharge.95 e Sn 3034 Sn 2840 Sn 2706 = 1.(4 KT_~_ 12 = A. I.C. = 3.

were also determined to check departures from the t’heoretical value of I .12 0.400 1.15 7.14 6.12 6.300 6.30 2.OO 6.46 8. this point was not examined in detail.32 2.56 2.700 1.33 2.300 0.14 0.he energy levels is not’ possible in t’he region of the catjhode layer. and 205 .400 2.900 1 1. and thermal equilibrium can be considered to exist.800 I 2. 2.000 ~6.23 0.600 1.700 6.12 ’ 5.800 1.11 ~ 6.16 . at t’he centre of the arc.400 ( 6.700 6.500 i T’K I 7. high-power. However.06 2.34 8. Ba II? and Mg I line pairs.16 6.000 / 0.5 mm from the elect’rode.12 0.he negative sample electrode for both the Type 2 discharge and the D. Relative intensities of the tin line pair 2840/2’706.12 I 2.ribution of the electron population among t.08 1 2.300 7.300 ~0.13 0.14 0.14 .The spectrochernical determination of impurities in copper and copper alloys are summarized in Table 2.39 I 8. They used Ba I.15 6.11 6.11 6.11 0.000 2.he excitation temperatures in a low-voltage.19 6.000 i 0. It’ is apparent from the large divergences in temperat’ure in the region next to t.C.48 “.11 0.700 0.88 i 13.700 6. CRAGGS.12 1.17 1 ( 12.800 6.500 6.12 6.11 0.0 . Table 2.17 2.16 2.otal light flux from the discharge was probably examined.400 1. As part of their explanation of this temperature discrepancy. arc: t’hat.700 1.14 0.0.000 0.000 6.09 1.9. t’he t.22 2.000+ 14.700 6.300 0. a Boltzmann dist.1’ 0. 15.100 1.97 I 1.13 0.600 6. On the other hand.88 13. temperatures computed from the two line pairs approach each other.11 0.11 0.000 6.000 . / 1.95 : I 2.15 0.000 6. 5.600 1.17 115. Consequently.500 6.10 1 5.95 1.33 ( 2.03 BRACDO.02 2.16 2.13 6.12 ) 6.000 __-___ 0.10 0. 6.16 2.97 I 14. This determination was not too successful for the spark-ignited arc-like discharge since the photographic density of Xn 2840 was greater t’han 2.11 ~6.29 i.21 7.200 Type 2 DC &PC 1. though not temperat’ure sensitive. Temperatures across discharge gap in mm Distance across gap RI Hn 326” Sn 3034 ( T’K I RI T”K RI ) T”K RI I T’K ~ RI 1 T”K RI ! 2.34 .000 0.16 2.17 2. and WILLIAMS [R] observed divergences in temperature almost idenOica1 to those in the cathode region in the course of an investigation of t.500 sn 2850 Sn 3034 ---DC arc Type 2 0.13 1. reference was made to the possibility that different zones of the discharge produced different populations in different energy levels. 2.98 1.400 ( 1.800 .09 IF6. Though not statSed explicitly.900 _____~_ 1.11 I ! 0. in this region other fact’ors in addition to t’emperature are operat’ing.25 2.000 1.27 7.300 0.000 6. triggered spark-arc source. at about 1 to 1.

C. This possibility was encouraged by the fact that many of the highly enhanced elements are the same elements which need to be detected in low concentration in copper and copper alloys. However. opened up the possibility of exciting large metal samples with a spark-ignited. and to have a value of 6900"-7100°Kfor the Type 2 discharge and 6300"-6500°Kfor the D. arc in sensitivity. In the investigation just described.FREDERICK V. if an analysis is to be practical for fast routine work. Determination of lead in brass and copper. 206 . any plate calibration or excitation standardization based on selected line pairs is of dubious value if the above factors are ignored.C.he adjustment of a critical optical system tend to throw the radiation from the cathode layer in or outside the ent. temperatures were found to be single valued in the region 1.5mm from the cathode to the anode in both cases. Consequently. line intensities with respect to background change with great rapidity in the cathode region. 6. Using the values of the t’in line pair 284012706 in the centre of the discharge as an emulsion contrast control.rance pupil of the optical system of the spectrograph. using the overdamped discharge. SCHATZ accurate microphotometer readings were not possible. When this was done. t. arc. 5. Since radiation from the cathode layer is several times more intense than that from the centre of the discharge. Errors arising from this situation are aggravated if slight changes in IO A7ttrg”tt--_j 1 i/iii]] % LEAD - Fig. A sensitive analysis of copper and copper alloys The enhanced relative sensitivity of many of the elements in the vicinity of the cathode or sample electrode. arc-like discharge equivalent to the conventional D. slight corrections were applied to the relative intensities of the other line pairs. its contribution to the total light flux would tend to be dominant in any optical condensing system that collects radiation from the entire discharge. optical adjustments and the position of the sample should not be so critical that it is difficult to maintain reproducibility.

The auxiliary curves designated by primed letters. In all cases these curves are linear. Shifts of the working curves? due either to a change in concentration of the 207 . no difficulty was experienced in reproducing the w-orking curves.ensity as a horizont’al asymptote.The spectrochemical determination of impurities in copper and copper alloys Consequently. 7. Determinat. in tests over a period of two years. 6 to 10 show working curves t’hat have been included to demonstrate the various analyses possible on copper alloys.h few exceptions. and their slopes. However. grave doubts were entertained regarding t’he suitability of a spectrochemical analysis based on enhancement at’ the cathode. background corrections are made. This device is quite useful when a limit. :: Fig. Once these auxiliary curves are obtained they can be used for extrapolating values on the uncorre&ed curves by adding the background relat*ive intensity to values along their extended range. Day-to-day checks were easily accomplished not only by means of the auxiliary lens system.004 0 Cl c. for careful work near the limits of relat.ed number of standards are available and t’he uncorrected working curve is to be used for analysis purposes. Since most of the curves are non-linear and approach 3. background corrections should a. However.ive sensit’ivity. but also by means of spectrographic line pairs whose relative intensities change rapidly in the cathode region. In many cases the most sensitive lines hare not been used.04 .lways be made. wit. are approximat’ely 45”. Figs.ion of iron in brass and copper background relative int.o:! IRON - 0. included in the various figures are obtained by correct’ion of the background of the analysis line only. during which the system was dismantled and reassembled many times.

5 % Pb BRASS 90-10 BRASS 0. 5.3 0. Such is the case in Fig. SCHATZ matrix element or to the presence of other elements. Changes in the length of the exposure time.04 % TIN Determination 0.FREDERICK V. Changes in the matrix element concentration. In many cases this shift’ occurs in a straightforward manner. Changes in relative intensity due to the effect of a change in concentration of the specific impurity on the intensity of the matrix element line. which are all out of proportion to the other elements. Studies of these shifts were hampered by an insufficient number of accurately analyzed standards. Consequently.1 0. In some cases shifts were so small that an average curve was drawn for the uncorrected curves. have been observed when tin. many of the curves are incomplete. silicon. amount of their additions. The following list is a brief resume of the observed causes for curve shifts. were observed and are indicated on many of the curves. 8.01 0.2 0. many of which are illustrated in the figures: 1.02 Fig. and aluminium are added to copper. 3. 8 where a single uncorrect’ed curve is drawn for tin. especially in the very low ranges of impurit’y concentration. Curve shifts of this type have been observed in copper where the presence or absence of minor impurity elements has an effect on the background.4 I of tin in brass and copper. 4. Changes in relative intensity of an impurity line due to the presence of Changes of this nature. This rather 208 . o 67-33 0 70-30 BRASS. 0. This effect can be eliminated by correcting both impurity and matrix lines for background. Changes in background intensity relative to the line intensity. 2. 0. but it is often complicated by the effects listed below. Curve shifts due to different rates of evaporation with time of the element in question and the internal standard copper may result from a change in exposure time.

This extremely annoying curve shift 209 3 . Determination of phosphorus in phosphor bronze and copper. relative intensities of different elements vary differently with increasing zinc content. Changes due to metallurgical effects.1 001 Fig. 7. 9.The spectrochemical determination of impurities in copper and copper alloys peculiar shift was observed in the determination of small amounts of iron in copper where increasing amounts of iron so enhanced the copper lines that the curve for relative intensity versus concentration was quite flat. Determination 0. 5 z E z 0.1 %ZINC of zinc in copper I. Changes in the volatility of the brass alloy with increasing amounts of zinc. Since copper is quite different from zinc in its susceptibility to at’tack by the discharge.0 and silicon-manganese bronze. [l] 6. 70 PHOSPHORUS - Fig. 10.

Z. M. 1924 29 356. J. J. Phys.. Met..7. Before especially noteworthy in the determination of phosphorus in copper. Amer. J. and WILLIAMS. O. Fe was present. SCHATZ has its origin from causes which are often obscure and difficult to locate. V.. and KEI+~P. [2] HASLER. and MCRAE.OOl~/. 210 . this method has been yellow brasses of high impurity content. 1938 16A 17. in the method described. gilding metal and In the conventional spark methods. Can. and is so heavy for pure copper that the entire spectrum is quite black.. Phys. ‘IT:.. M.. Spectrochim. G. However. Any D. using the light emitted over the copper. using the present procedure. F.. Opt. C. G.C. Sot. Res. Proc. well above the Fe content of most refined copper. [7] LANGSTROTH.. J. D. G. [3] Applied Research Laboratories Newsletter 1951 4 2. J. Also it differs from the preceding shifts in that it is often random in its occurrence. which uses a selected portion of a special type of discharge from the Multisource. Inst. In general the method has displayed the greatest improvement in sensitivity over conventional spark methods in the analysis of red brass. [8] BRAUDO. Acta 1949 3 546. Inst. Fe 2535. in the present method Fe 2535. copper is handled with the same ease as the As an example. J. background builds up with increasing copper content very rapidly.. R. Sot. [4] HANSEN.. References [l] SCHATZ. M. Lond. no excitation conditions could be found that gave consistently good results for a phosphorus content of 0.01 to 0.6 is suppressed and does not appear until Fe reaches O-O15o/o. 1947 59 273. [5] MILBOURN. CRAGGS. Met.. 1952 80 77. D. entire discharge.FREDERICK V. 1943 99 441. J. [6] MILBOURN. 1944 34 21. A. the most sensitive phosphorus line. arc excitation methods were also complicated by the fact that when O.05% in copper due to variations in the relatively strong background present.6 interferes with P 2535. However. F.