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O x: , , _ . .)r Ivaz‘fl . C. {fivlsli ,:J-L;.~nr.-lpr ‘ SENSITOMETRIC STUDIES OF SOME EOSITIVE EMULSIUNS AND THE AVAL’HTION OF CHARACTERISTIC CUEBTANTS BY Edward A. Rominski Submitted in partial fulfillment of the requirements for the degree of Master of Science in the Graduate School, Michigan State College Department of Chemistry. June, 1959 Appreciation The writer wishes to express his appreciation to Dr. D. T. Ewing for his helpful suggestions and guidance during the course of this investigation. 121489 SENSITOMETRIC STUDIES OF SOME POSITIVE EMUISIONS AND THE EVALUATION OF CHARACTERISTIC COLSTAMTS Photographic materials are classified very largely, both by the manufactures and by those who use them, with respect to that quality which is designated as "contrast". The trade names by which these materials are known con- tain some Specifications of the contrast characteristic. Among the terms used are hard, soft, normal, medium, contrast, vigorous, etc. For the purpose of classification and as an indication of adaptability to various purposes, especially true reproduction of spectographic lines, a knowledge of the contrast of a printing paper is probably of greater importance than that of any other of its char- acteristics. The meaning of the term "contrast" as applied to printing paper, while understood in a general way by the lmanufacture, is somewhat difficult to define. In fact, the same word when applied to different brands of paper may indicate widely different contrast characteristics. The use of such terms for the specification of this very important characteristic is obviously inadequate, and it seems highly desirable to find some method whereby "contrast" can be measured precisely and specified in numerical terms. The possibility of using various sensitometric constants of a printing paper for obtaining an eXpression of contrast has been considered by many experiments in the photographic field, and several proposals hav 6 been made. Jones, Mesa, and Nuttingl were the first to attempt to apply to photographic materials the sensitometric methods originated by hunter and Driffieldz to determine their characteristics. The blackness of the silver de- posit was defined in a manner similar to the density values commonly used when dealing with the light-transmitting materials, the logarithm of the reciprocal of the diffuse reflection being defined as reflection density; This method of defining reflection density is in agreement with that proposed by Renwick3 and used by him in a study of the relation between the density values of silver deposits when measured by reflected and transmitted light. Formstecher4’5 has treated the subject of contrast especially from the standpoint of exposure latitude and of the relations existing between the characteristics of the negative and printing paper. While he did not make any definite prOposal for the specification of contrast, his treatment of the subject is of general interest. Kiesser6 after describing the well-known.nunter and Driffield method of expressing the characteristics of photographic 3 materials, proposed that the slope of the straight line portion to be taken as a measure of contrast or graduation. He suggests that the angle which the straight line port- ion makes With the log Exposure-axis, expressed in degrees be used as a numerical specification, Hallv’8 proposed that the value of total scale be used as a means of express- ing contrast and Taylor9 also proposed the use of total scale, but in the reciprocal form and multiplied by a constant in order to obtain a series of whole numbers. Glover10,11,12,1s has treated the subject very carefully from.the sensitometric standpoint and emphasized the fact that exposure scale alone is quite inadequate as an expression of contrast. He concludes that values of 'gamma infinity', 'total scale','maximum density', and 'rendering power' are necessary for a complete specification of contrast. Of these he believes 'gamma infinit y' to be of greatest importance and 'total scale' of almost as great a value. His final conclusion is that it is rather hepeless to attempt any expression of contrast in the form of a single numerical value. As an alternative plan he proposed the use of a multiple test-negative, consistiong of six negatives, varying in contrast, from which test points can be made on various papers and a scale of six contrast steps be thus established. From.this review of literature it was decided to de- termine sensitometrically the value of:- (1) Maximum density (2) Gamma, (3) Total Scale, (4) Latitude, and (5) Rend- ering power, for various groups of printing paper, in order that this adaptability to the printing of spectro- graphic plates be better understood. Definition of Sensitometric Terms Opacity, Density, and Transparency hunter, and Driffieldz first stressed the importance of defining clearly opacity, density, and transparency, since the mathematical relationship of these qualities, one with another, forms the basis of sensitometry. Opacity was defined by them as the power of a substance to resist the passage of light, or simpler still, as the ratio between the unit of entering light, and the fraction allowed to emerge. Transparency is the inverse relation or may be de- fined as the reciprocal of opacity. Density is more difficult to define, because it is in effect, synonymous wi th opacity, the difference, being that while both terms define blackening is respect of a photographic emulsion, density implies the Specific degree of blackening, or light stopping substance, and is a measure of the quantity of metallic silver deposited per unit area. The Lambert-Beer law, Density = loglo (opacity) = -log10 (transparency), of absorption of light includes the state- ment that absorption increases in geometrical progression as the thickness increases in arithmetical progression, and in applying the argument to a series of densities occurring in a photographic negative, hunter and Driffield revealed the set of conditions which gave rise to the characteristic curve. Characteristic Curve A typical characteristic curve for paper is here shown in figure 1. This curve is obtained by plotting the reflection densities of the paper obtained by full developement against the logarithm of the exposures that give rise to them. The reflection densities of a paper are measurements fulfilling the equation .1. p R where R is the reflecting power measured when the silver Density I log deposit on the paper is illuminated by a narrow pencil of light at an angle of 45° and viewed at an angle of 90°. The measurement is analogous to the H. and D. density measurement in the case of plates where D: log 5%, T being the transparency of the silver deposit under measurement. The characteristic curve of a paper derived in this manner exhibits the following features:- Total Scale (Exposure Range or Exposure Scale). In Fig. 1 an eXposure Ea gives rise to the faintest descernible tone upon the paper and Eb gives rise to the deepe st black. Then the quantity log Eb - log Ea gives the total scale of the paper. It is the range of exposure which enables the paper to record all possible tones from the faintest gray to the deepest black upon‘full developemnt. The usual condition of successful printing is that the total scale of the paper in logarathmic units should be equal to or slightly greater than the density scale of the negative. Whereas two papers with the same total scale my yield similar points from the same negative, two papers with different total scales can never yield points of the same appearance from the same negative. The total scale is, therefore, an import- ant measurement descriptive of one feature of the chara- cteristic curve of the paper. Gamma:- As in the case of plates, so in the case of papers, the straight line portion of the characteristic curve (0 d in.Fig 1.) when produced downward will intersect the exposure axis at an angle (°< in Fig l.) The tangent % is the gamma of a paper . It is known that the gamma of a paper increases as its developement progresses in the same manner as it does in the case of plates, yet after a com- paratively short time of developement, the gamma obtained is the maxmium.gamma of the paper and further developement occassions no further increase. The gamma of a paper is there- fore the gamma infinity (BLJ of that paper. Maximum Density:- The maximum density of the paper (Ema! 1n.Fig l.) is a measurement of great importance. Other things being equal the deeper the black that a paper will yield, the more it is for practical point production. The surface of the paper has a marked influence upon this measurement. With similar emulsions the depth of black is determined by the "glossiness" of the paper surface: the more glossy it is the more deeper the black recorded. With similar paper surfaces the depth of the black is determined by the nature of the emulsion: the deeper the black the better the emulsion. It is necessary, therefore, to add the measure of the maxi» mum density (black) to the constants total scale and gamma already'nentioned. Exposure Latitude:- The exposure latitude of a paper is the range of ex- posures that lie on the straight line portion of the characteristic curve. In.Fig l. c to d is this straight portion and subtends an exposure scale from Log Ea to log Ed' Between these points the ratio of the increase in density to increase in exposure is constant. Rendering Power:- By this term.is meant the capacity of a paper to re- produce the negative graduations with relative fidelity. Relatively true reproduction is confined to the tones which lie upon the straight line portion of the paper curve. Other things being equal, the paper with the longer straight line portion of the characteristic curve in comparison with the total length of the curve is the better paper. In Fig l. the whole curve ab subtends an exposure scale from.log Ea to 10gb. Of this whole curve the portion cd is straight and has an eXposure latitude of logEc to log Ed. The rendering power is log Ed to log Eo and, being a fraction, it is multiplied by log Eb -‘logTEE 10 for convenience. Very few papers have more than half their total curve straight equivalent to a rendering power of t or if multiplied by 10 equal to 5. A poor paper may have a rendering pwwer of less than 2, indicating that it is capable or rendering by few tones with truth at one and the same line. Papers may have the same total scale and the same maximum density, but lacking coincidence of the curves will indicate thatprints upon them.from the same negative would differ. The five constants described would by their quality indicate with a fair degree that the paper curves were identical and similar paints could be expected from the same negative. Summarized, they are the measurements of: (l) Maximum.density (Dmax (2) Slope of straight line (2(=gamma) (3) Total Scale (4) Latitude (5) Rendering power No one of these constants is descriptive of the quality of the paper to be an indication of the print that it would yield. 10 Experimental Determination of Constants Material In order that the contrast values cover as large a range as possible, twenty-one various kindss of printing papers of both the chloride and bromide emulsions repre- senting a great range in characteristics were eXposed. An attempt is made in Table l to state in a general way the physical characteristics of the materials. The columns designated as surface, thickness, and color contain approximate specifications of these values, and in the last column the contrast as designated on the package by the manufacture. 11 Table I Physical Characteristics of Papers Used Name Surface Thickness Color Contrast Azo E Semi-matle SW White 0 Azo E Semi-matle SW White 1 A20 E Semi-matle SW White 2 A20 E Semi-matle SW White 3 A20 E Semi-matle SW White 4 A20 E Semi-matle SW White 6 Velez F Glossy SW White 1 Velox F Glossy SW White 8 Velox F Glossy SW White 3 Velox F Glossy SW White 4 Velez F Glossy SW White 5 P.M.C. 2 Semi-matle SW White Normal P.M.C. 2 Semi-matle SW White medium PMM.C. 2 Semi-matle SW White Contrast P.M.C. 2 Semidmatle SW White Extra Contrast Kodabrom.F Semi-matle SW White 1 Hodabrom F Semi-matle SW White 2 Kodabrom.r Semi-matle SW White 3 Kodabrom F Semi-matle SW White 4 Viteva Opal B Semi~matle nw $3932 Fall Scale Vitave Opal C Semi-matle DW Cream. F311 Scale White 12 Exposure Since exposure is a product of intensity and time of action of light, the series of exposures were obtained as follows: In order to provide a sufficient number of points for the precise determination of the shape of the characteristic curve a tablet containigg a series of known densities, known as a "stepawedge" was employed. This tablet was purchased from Eastman Kodak C. and the densi- ties of this step wedge increased regularly from step to step, so that the intensities transmitted decreased logarithmically, and the increments of exposure represented by equal segments of the "log E" axis and were of the power of the 14f.' The calibration of this tablet was done on an Eastman Densitometer and appears in Table II and Fig. 2. Owing to the light-scattering properties of the silver particles, the effective printing densities of thw wedge varies according to the type of exposure, emplnyed- projection or contact- and in order to eliminate variation, the contact or diffused densities of the wedge were measured, and the material exposed in contact with the wedge. To limit the area of the material eXposed a set of opaque masks of the same dimensions as the paper was provided in which are cut apertures of various dimensions, the area of the aperture increasing from.mask to mask. The wedge, masks and material to be exposed were placed in a holder at a distance of 2 meters from the Table II Step-Tablet Calibration Step Rel. E2posure Log10 E Density 1 l 0 .04 2 1.414 .149 .19 3 2 .301 .33 4 2.82 .450 .48 5 4 .602 .63 6 5.64 .751 .78 7 8 .903 .92 8 11.28 1.053 1.07 9 16 1.204 1.22 10 22.5 1.352 1.37 11 32 1.505 1.52 12 45 1.653 1.67 13 64 1.806 1.82 14 90 1.954 1.96 15 128 2.107 2.11 16 180 2.255 2.26 17 256 2.408 2.41 18 360 2.556 2.56 19 512 2.709 2.70 20 720 2.857 2.85 21 1024 3.011 3.00 14 light source, so that the intensity incident upon all portions of the wedge was substantially constant. Ex; traneous reflections were excluded by placing the source at the end of a black cardboard tube. The source used for both chloride and bromide papers was an unfiltered electric filament and a 100 watt for the bromide. The ex- posures for each strip increased geometrically and were carefully timed with a stOp watch at 4-8-16-32—64-128 seconds for the chloride and 15-30-60-120-240-480 seconds for the bromide papers. 15 Processing Technique (a) Choice of "standard" developer In photographic practice different types of material often require different types of deve10pers in order to produce their characteristic results. A developer made in accordance with a given formula would therefore give very unreliable in- formation of the practical photographic properties of a material if it were universally applied as a sensitometric standard developer. Even for any one type of material a considerable range of develOpers is recommended by the various manufactures and used in practice, each developer producing a different photographic result. No convention has yet been reached, and the choice of a "standard" developer is left to the individual sensitometric worker. Therefore, in this sensitometric study, develOpment of the prints was carried out in‘a solution known as D-72 compounded in accordance with a well-known manufacturer's instructions. . The choice of deve10per having been made, it was essential that the composition and temperature of developer and time of develoPment should be most accurately controlled. (b) Development Since the composition of a developer changes during deve- lopment, no more than one batch of material (a batch representing a quantity developed at the same time)_was passed thru a diSh of developer. The constituents of a batch was spread out so 16 that no super-position of one portion upon another occurs, and treated so that fresh developer was continually applied to the surface of the material, and products of development continuously removed. The latter conditions were achieved most simply by continuously brushing the surface of the material with a camel hair brush. Finally the ratio of volume of developer to quantity of material developed was sufficient to ensure that the activity of the developer does not fall off appreciably during development. Developing time was sufficiently long enough to result in complete develOpment (this condition of complete development may be defined as the minimum development time resulting in the maximum density and maximum gamma obtain- able). All portions of the material was totally immersed during development. The procedure of sensitometric development: a developer of the following formula was used as a "standard developer": Elon-Hydroquinone developer (formula D-72) Water (52°C) 500.0 c.c. Elon 3.1 grams Sodium.Su1phite, desiccated 45.0 " Hydroquinone 12.0 " Sodium Carbonate, desiccated 67.5 " Potassium Bromide 1.9 " Water to make 1 liter For use, part of the above stock solution was mixed with. 2 parts of water for the chloride papers, and a 1-4 dilution 17 for the bromide. The temperature of this solution was kept constant at 21°C during development. The time of development was that recommended by the paper manufacturer (45 seconds for chloride and 90 seconds for bromide) and was carefully maintained by the use of a step-watch. 1‘he sensitometric strips were placed side by side in the tray, and not less than 250cc of developer used per 8 x 10-inch sheet of material. The surface was brushed continuously by a camel hair brush, which passed over every portion at least once every five seconds. (0) Fixation Immediately after development was complete, the material was rapidly transferred to an acid stop bath, dilute acetic acid, followed by a brief wash and fixation in acid hardening fixing bath for 20 minutes. The temperature of the fixing bath was never allowed to exceed 21°C. and was discarded after fixing thirty 8 x 10-inch sheets per liter. (d) Washing After fixation, the material was removed to a large tray and washed for at least one hour in cold running tap water which flowed rapidly enough to replace the water in the tray 10 to 12 times per hour. The prints were separated several times during this period. (e) Drying When washing was complete, the prints were removed and the excess water allowed to drain off. They were then placed 18 between layers of cheesecloth and allowed to dry. The measurement of Densities It was shown previous that density is optically defined as the logarithm of the Opacity, which in turn is defined as the ratio of the incident intensity to the transmitted or reflected intensity. To accuratly measure this reflected intensity a modified Capstaff—Purdy densitometer manufactured . by Eastman Kodak Co., was employed. As papers differ slightly from each other in reflecting powers of the stock, the reflection density values were com- pared with that reflected from the plain stock obtained by fixing the undeve10ped material as zero. For measurement a small area 4mm., is illuminated by nearly parallel light at 45° to the surface, and the intensity of the light reflected normally from the photographic deposit is measurement by comparison to the intensity transmitted by a standard calibrated comparison wedge. 19 Evaluation of Constants The densities of the sensitometric strips having been determined the characteristic curves were plotted for each paper. These curves are shown in Figs. 3,4,5, and6. The values of the various constants were evaluated as described in the section-~Opacity, Density, and franency and tabulated in Table III where they can be compared conveniently with each other. It will be noted that the maximum density is approximately the same for each group of papers. The slight variation occur- ing in this value is undoubtedly due to the fact that the age of the papers were not the same and the difference was enough to influence the characteristic constant. If perfectly fresh paper could have been obtained this variation would vanish. 20 Table III Characteristic Constants of Positive materials Name Contrast Total Latitude 25’ Maximum Rendering Scale Density Power 420 E 0 1.806 .755 1.35 1.52 4.18 A20 E 1 1.505 .602 1.48 1.53 4.00 Ase E 2 1.355 .525 1.68 1.57 3.88 A20 E 3 1.204 .450 2.07 1.57 3.73 Azo E 4 1.056 .301 2.36 1.56 2.85 120 E 5 .755 .149 3.12 1.58 1.97 76101 F 1 1.806 .602 1.96 2.00 3.33 7610! F 2 1.654 .525 2.52 2.02 3.17 Velox F 3 1.504 .449 3.19 1.98 2.99 V0102 F 4 1.051 .301 3.37 1.95 2.89 76101 F 5 .750 .149 4.78 2.08 2.00 P.MkC. 2 N' 1.504 .750 1.44 1.47 4.97 P.M.C. 2 MI 1.352 .602 1.54 1.42 4.45 P.M.C. 2 0 1.204 .449 1.98 1.42 3.73 PdM.C. 2 EC 1.204 .301 2.12 1.41 2.50 Kodabram 1 1.657 .602 109 1.40 3.64 Kodabrom 2 1.505 .525 129 1.40 3.49 Kodabrom 3 1.355 .450 147 1.40 3.33 Kodabrom 4 1.056 .301 2.06 122 2.88 Vitava Opal B Exposure not sufficient 1'52 Vitava Opal C .99 to evaluate constants. 21 Summary 1. The contrast or printing quality of a paper can be fully described by the measurement of: (a) Maximum density (b).Gamma (c) Total scale (d) Latitude (e) Rendering power or these five constants the gamma measurement is essential, the total scale and latitude very desirable, and the remaining two helpful as far as reproduction is concerned. For successful tone reproduction the density scale of the negative should be less than the total scale and greater than the latitude of the printing paper. A stale or semi-stale paper should not be relied upon to possess the same characteristics as when fresh. 1. 2. 3. 4. 5. 6. 7. 22 Bibliography Jones, L. A., Mees, E. C. K., and Nutting, P. 0.: ”Sensitometry of Photographic Papers," Phot. Jour., 349, 1914. Hurter, P., and Driffield, 7.0.: "Relation between Photographic Negatives and Their Positives,” Jour. Soc. Chem. Incl., 10, 100, 1891. "Photo- graphic Investigations and a Newimethod of Determination of the Seneitiveness of Photographic Plates," Jour. Soc. Chem. Incl., 9, 455, 1890. Renwick, F. F. : "The Under-Exposure Period in Theory and Practice,” Phot. Jour., 37, 127, 1913. Pornsteoher, Felix: "Die Absolute Gradation als Charakteristische Konstante Photographischer Papiere," Leit. wise. Phot. 22, 21, 1922. Formstecher, Felix: "Der Belichtungs spielraum.der Photographischen Entwicklungs papiere, ' Phot. Incl., 79, 1918. Kisser, K. : "Die Gradations-Bezeichmengon Photo- graphische Papiere," Phot. Incl., 424, 1920. Hall, J. R. : ”A Contrast Rating for Printing Papers,” Brit. J. Photo., 68, 407, 1921. 8. 9. 10. 11. 12. 13. 14. 15. 16. 17. 23 Hall, J. R. : "The Vigor of Printing Papers, " Amer. Phot., 12, 1922. Taylor, H. : ”A Contrast Rating for Bromide Papers," Brit. J. Phot., 68, 694, 1921. Glover, B.J.T. : "A contrast Rating for'Printing Papers," Brit. J. Phot., 68, 694, 1921. Glover, B.J.T. : ”A Contrast for Rating Bromide Papers," Brit. J. Phot., ca, 723, 1921. Glover, B.J.T. : "The Contrast Rating of Gaslight and Bromide Papers,“ Brit. J. Phot., 69, 156, 1922. Glover, B.J.T. : Brit. J. Phot., 69, 23, 1922. Rayleigh, Lord : "0n the General Problem of Photographic Reproduction," Phil. Mag., 22, 734, 1911. Renwick, F.F. : ”The Fundamental Law for the True Photographic Rendering of Contrast,” Phil. Mag. 38, 633, 1919; 39, 151, 1919. Jones, 1.1. : ”Photographic Rendering of Tone Values," J. Frank. Inst., 189, 469, 1920. Jones, L.A. : ”The Contrast of Photographic Printing Papers," J. Frank. Inst., 202, 177, 1926; 203, 111, 1927; 204, 41, 1928. 24. 18. Hopkinson, R.C. : "A New Approach to the Problem of Tone Reproduction," Phot., J. 77, 542, 1937. 19. Renwiok, F.F. : ”Difficulties in Translating the Theory of Tone Reproduction into Practice and Contrast.” Phot. J., 77, 7, 1937. 20. Abribat, M. : ”Considerations generales sur le renche photographique des 1uminosites." Rev. d'Optique, 14, 40, 1935. 21. Bontenbal, J. : ”Some Investigations on the Contrast of Photographic Positive Papers,” Phot. J., 78, 76, 1938. mama‘s U=.E<~._OO._.O_.E QM EN 1N _.N masoodxm 09 Q. n. N. no M250 QFflm—EUgIU a. 0. 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