CN106842807B - Chemical sensitization method of silver halide emulsion - Google Patents
Chemical sensitization method of silver halide emulsion Download PDFInfo
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- CN106842807B CN106842807B CN201510888466.4A CN201510888466A CN106842807B CN 106842807 B CN106842807 B CN 106842807B CN 201510888466 A CN201510888466 A CN 201510888466A CN 106842807 B CN106842807 B CN 106842807B
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- silver halide
- barium
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- halide emulsion
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 63
- 239000004332 silver Substances 0.000 title claims abstract description 63
- -1 silver halide Chemical class 0.000 title claims abstract description 63
- 239000000839 emulsion Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 25
- 206010070834 Sensitisation Diseases 0.000 title abstract description 61
- 230000008313 sensitization Effects 0.000 title abstract description 61
- 239000000126 substance Substances 0.000 title abstract description 46
- 239000008273 gelatin Substances 0.000 claims abstract description 51
- 108010010803 Gelatin Proteins 0.000 claims abstract description 49
- 229920000159 gelatin Polymers 0.000 claims abstract description 49
- 235000019322 gelatine Nutrition 0.000 claims abstract description 49
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 49
- 238000000498 ball milling Methods 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 30
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical class [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims abstract description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910001632 barium fluoride Inorganic materials 0.000 claims abstract description 7
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 4
- 230000008014 freezing Effects 0.000 claims abstract description 3
- 238000007710 freezing Methods 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 17
- 229910052788 barium Inorganic materials 0.000 claims description 15
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 12
- 230000001235 sensitizing effect Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 6
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 claims description 2
- HOLVRJRSWZOAJU-UHFFFAOYSA-N [Ag].ICl Chemical compound [Ag].ICl HOLVRJRSWZOAJU-UHFFFAOYSA-N 0.000 claims description 2
- 230000035800 maturation Effects 0.000 claims 1
- 239000010931 gold Substances 0.000 abstract description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 10
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052737 gold Inorganic materials 0.000 abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 5
- 206010034960 Photophobia Diseases 0.000 abstract description 4
- 208000013469 light sensitivity Diseases 0.000 abstract description 4
- SOHDHMRBRGSXMV-UHFFFAOYSA-N [Ba].FOF Chemical compound [Ba].FOF SOHDHMRBRGSXMV-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 abstract description 3
- 239000002019 doping agent Substances 0.000 abstract description 2
- MSQCWIHWHAEZLC-UHFFFAOYSA-N [Ba].BrF Chemical compound [Ba].BrF MSQCWIHWHAEZLC-UHFFFAOYSA-N 0.000 description 23
- 230000035945 sensitivity Effects 0.000 description 18
- RBRFDGCVTRKUEW-UHFFFAOYSA-L barium(2+);chloride;fluoride Chemical compound [F-].[Cl-].[Ba+2] RBRFDGCVTRKUEW-UHFFFAOYSA-L 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000003384 imaging method Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000011161 development Methods 0.000 description 5
- 230000010198 maturation time Effects 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- 238000000424 optical density measurement Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- YERYEKFNDGFHJE-UHFFFAOYSA-N FI.[Ba] Chemical compound FI.[Ba] YERYEKFNDGFHJE-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- FHOMZPIQIJQCHD-UHFFFAOYSA-K [I+].[F-].[Ba+2].[F-].[F-] Chemical compound [I+].[F-].[Ba+2].[F-].[F-] FHOMZPIQIJQCHD-UHFFFAOYSA-K 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XEIPQVVAVOUIOP-UHFFFAOYSA-N [Au]=S Chemical compound [Au]=S XEIPQVVAVOUIOP-UHFFFAOYSA-N 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
- 229940075444 barium iodide Drugs 0.000 description 1
- 229910001638 barium iodide Inorganic materials 0.000 description 1
- DJTDNMUUJVALPC-UHFFFAOYSA-L barium(2+);fluoride;iodide Chemical compound [F-].[I-].[Ba+2] DJTDNMUUJVALPC-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000090 biomarker Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 238000006380 bromofluorination reaction Methods 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000000799 fluorescence microscopy Methods 0.000 description 1
- OMRRUNXAWXNVFW-UHFFFAOYSA-N fluoridochlorine Chemical compound ClF OMRRUNXAWXNVFW-UHFFFAOYSA-N 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Conversion Of X-Rays Into Visible Images (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
The invention discloses a chemical sensitization method of silver halide emulsion. Adding a gelatin solution containing halogenated barium fluoride particles subjected to ball milling into a silver halide emulsion at a constant temperature of 45-55 ℃, wherein the adding amount of the gelatin solution isAccording to the addition of 1 x 10 per mole of silver in the silver halide emulsion‑3～1×10‑6And (3) stirring for 20-80 minutes according to the molar halogenated barium fluoride, and then quickly freezing and storing. The invention discloses a fluoride-halogen barium fluoride (BaFX: Eu) doped with rare earth ions for the first time2+) (X ═ Cl, Br, I) as a dopant, was introduced into a silver halide emulsion to prepare a barium oxyfluoride (BaFX: eu (Eu)2+) Compared with the conventional chemical sensitization of the sulfur and gold, the chemical sensitization of the silver halide emulsion after chemical sensitization can improve the light sensitivity by 2 times, and the fog is not increased.
Description
Technical Field
The invention relates to the technical field of photosensitive materials. And more particularly to a highly efficient chemical sensitization method for silver halide emulsions.
Background
Although the highest pixels of cameras used in digital technology have reached hundreds of millions in recent 20 years, have relatively high sensitivity and excellent imaging quality, and have taken the place of silver salt photography to dominate the civil market, in special imaging fields, digital photography technology has not been able to obtain sufficiently clear visible images, and the sharpness of the images becomes worse after the image is enlarged. The high-sensitivity silver halide emulsion can easily and freely obtain the fine and soft observation image with high image quality. The intensive research and improvement of the preparation and sensitization technology of the special ray silver halide photosensitive material to improve the light sensitivity, the imaging quality and the like still remain the main work which needs to be done in the imaging science community at present.
The current literature reports that the sensitization means of silver halide photosensitive materials include conventional chemical sensitization (e.g., sulfur sensitization, gold sensitization, and sulfur-gold combined sensitization), spectral sensitization (e.g., green sensitization, blue sensitization, and red sensitization), hole-electron conversion sensitization technology (e.g., silver dimer converter, carboxylic acid-type hole converter, and two-electron donor compound converter that can be split into molecular fragments) (summerge, national red, yawne, zhao culture, holes and their conversion during latent image formation, sensitization science and photochemistry, 2002, 20(1):46-59), and Hydrogen over sensitization (Hailstone R K, Liebert N B, Levy M, mccleararyr T, gimolol S R, Jeanmaire D L, Boda C R. achievev High Quantum yield with moisture sensitization, 1. 1988, 19832, etc.).
Rare earth ion doped fluoride micro-nano luminescent materials have received much attention in recent years (factory and controllable synthesis of monodisperse CaF)2and CaF2:Ce3+/Tb3+hollow spheres as efficient luminescent materials and smart drug carriers[J]Chem. eur.j., 2010,16(19):5672-5680.) has the advantages of narrow emission peak, high luminescence quantum yield, stable and durable luminescence, and the like, and shows good application prospects in the aspects of lasers, displays, fluorescence imaging, biomarkers, and the like. Such as BaFX: eu (Eu)2+(X ═ Cl, Br and I), the best X-ray storage phosphor, can be used in X-ray intensifying screens and computer radiation Imaging (CR) Imaging Plates (Imaging Plates, IPs) (Physics and current understating of X-ray storage phosphors [ J ]].Phys.Status.Solid.A，2001，187(2):335-393)。
It is necessary to provide a chemical sensitization method of silver halide emulsion by improving the preparation of silver halide photosensitive material and sensitization technology to improve the sensitivity and imaging quality.
Disclosure of Invention
It is an object of the present invention to provide a method for chemically sensitizing silver halide emulsions. Compared with the silver halide emulsion chemically sensitized by the conventional sulphur plus gold, the silver halide emulsion chemically sensitized by the barium halogen fluoride has the advantages that the light sensitivity can be improved by 2 times, and the fog is not increased.
In order to achieve the purpose, the invention adopts the following technical scheme:
a chemical sensitization method of silver halide emulsion at 45-55 deg.CAdding the gelatin solution containing the halogenated barium fluoride particles after ball milling into the silver halide emulsion at constant temperature, wherein the adding amount is 1 multiplied by 10 according to the addition amount of each mol of silver in the silver halide emulsion-3～1×10-6And (3) stirring for 20-80 minutes according to the molar halogenated barium fluoride, and then quickly freezing and storing. The molecular formula of the halogenated barium fluoride is represented as BaFX: eu (Eu)2+(X＝Cl、Br、I)。
Preferably, the preparation method of the gelatin solution containing the barium halofluoride particles after ball milling comprises the following steps:
1) uniformly dispersing the barium halofluoride powder in a gelatin aqueous solution and carrying out ultrasonic treatment;
2) and pouring the uniformly dispersed barium fluoride halide gelatin aqueous solution into a ball milling tank for ball milling to obtain the gelatin solution containing barium fluoride halide particles.
Preferably, in the step 1), the mass percentage concentration of the barium halofluoride in the gelatin aqueous solution is 1-10%.
Preferably, in the step 1), the mass percentage concentration of the gelatin aqueous solution is 1-6%.
Preferably, in the step 2), the ball milling speed is 200-600 r/min, and the ball milling time is 15-30 hours.
Preferably, the size of the barium oxyfluoride particles in the gelatin solution containing the barium oxyfluoride particles after ball milling is in the range of 1.0 to 10.0 microns, and the size distribution is narrow.
Preferably, the silver halide morphology in the silver halide emulsion is one or more of cubic, octahedral, spherical and T-particle.
Preferably, the silver halide in the silver halide emulsion is one or more of silver chloride, silver bromide, silver bromoiodide, silver chlorobromide and silver chloroiodide.
So far, no literature reports that the fluoride micro-nano material doped with rare earth ions can be applied to the research and development of silver halide materials in the field of photosensitive chemistry, particularly the preparation and sensitization of silver halide emulsions. The applicant of the present invention has conducted extensive studies by uniformly dispersing a rare earth ion-doped fluoride-barium halofluoride in a gelatin solution and then using spheresThe particle size of the silver halide emulsion is controlled to be 1.0-10.0 microns by grinding, and the silver halide emulsion is doped at the addition amount specified in the invention (the addition amount is 1 multiplied by 10 according to the addition amount of silver in each mole of silver in the silver halide emulsion-3～1×10-6Calculated for molar halogenated barium fluoride), to produce a halogenated barium fluoride (BaFX: eu (Eu)2+) Compared with the conventional chemical sensitization of the sulfur and gold, the chemical sensitization of the silver halide emulsion after chemical sensitization can improve the light sensitivity by 2 times, and the fog is not increased.
The invention has the following beneficial effects:
the invention discloses a fluoride-halogen barium fluoride (BaFX: Eu) doped with rare earth ions for the first time2+) The silver halide emulsion after chemical sensitization by barium halofluoride is prepared by introducing (X ═ Cl, Br and I) as a doping agent into the silver halide emulsion, and compared with the conventional chemical sensitization by sulfur and gold, the sensitivity of the silver halide emulsion after chemical sensitization can be improved by 2 times, and the fog is not increased.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
(1) 4 g of barium bromofluoride (BaFBr: Eu) are first introduced2+) The powder was dispersed in 200 ml of a 7% gelatin aqueous solution by mass percentage, and then subjected to ultrasonic treatment at normal temperature to convert barium bromofluoride (BaBrF: eu (Eu)2+) The particles are uniformly dispersed in the gelatin water solution; wherein barium bromofluoride (BaBrF: Eu)2+) The mass percentage concentration of the gelatin aqueous solution is 2 percent.
(2) Uniformly dispersed barium bromofluoride (BaBrF: Eu)2+) Pouring the aqueous solution of gelatin into a ball milling tank for ball milling, and using 100 gelatin500 pieces ofBall-milling the zirconium oxide pellets at the rotating speed of 200 revolutions per minute for 15 hours to obtain a gelatin aqueous solution containing barium bromofluoride with the diameter of about 10 microns and narrow particle size distribution;
(3) at 45 ℃, adding 10 ml of barium bromofluoride gelatin aqueous solution which is obtained after ball milling and has the diameter of about 10 microns and narrow particle size distribution into 100 g of cubic silver bromide emulsion, wherein the adding amount is 1 multiplied by 10 according to each mol of silver in the silver halide emulsion-3After the maturation time was 20 minutes in terms of the molar barium bromofluoride, smear, exposure, development and fixation processing and optical density measurement were performed under a dark room condition, and the following sensitivity data were obtained. The data pair ratios of the method of this example and the conventional chemical sensitization method for S-Au are shown in Table 1.
TABLE 1
| Mode of intensifying | Chemical sensitization of conventional S-Au | Chemical sensitization of barium bromofluoride |
| Sensitivity of light | 75 | 150 |
| Fog mist | 0.08 | 0.08 |
| Coefficient of contrast | 0.65 | 0.5 |
The data in the table show: barium defluorinated bromide (BaBrF: Eu)2+) Compared with the conventional chemical sensitization of the sulfur and gold, the chemical sensitization of the silver halide emulsion after chemical sensitization can improve the sensitivity of the emulsion by 1 time, fog is not increased, and the contrast coefficient is slightly reduced.
Example 2
(1) First 8 grams of barium chlorofluoride (BaFCl: Eu)2+) The powder is stirred and dispersed in 200 ml of gelatin aqueous solution with the mass percentage concentration of 7 percent, and then ultrasonic treatment is carried out at normal temperature, so that the barium chlorofluoride particles are uniformly dispersed in the gelatin aqueous solution; wherein the mass percentage concentration of the barium chlorofluoride in the gelatin water solution is 4 percent.
(2) Pouring the uniformly dispersed barium chlorofluoride gelatin aqueous solution into a ball milling tank for ball milling, and utilizing 100 pieces of the aqueous solution500 pieces ofThe zirconia balls are ball-milled at the rotating speed of 300 revolutions per minute for 20 hours to obtain gelatin aqueous solution containing barium chlorofluoride with the diameter of about 8 microns and narrow particle size distribution;
(3) at 48 deg.C, adding 10 ml of the above gelatin aqueous solution containing barium chlorofluoride with diameter of about 8 microns and narrow particle size distribution obtained by ball milling into 100 g of octahedral barium chlorofluoride emulsion at 1 × 10 per mol of silver in silver bromoiodide emulsion-4After the maturation time was 40 minutes in terms of molar barium chlorofluoride, smear, exposure, development and fixation processing and optical density measurement were performed under a dark room condition, and the following sensitivity data were obtained. The data pair ratio of the method of this example and the conventional chemical sensitization method of S-Au is shown in Table 2.
TABLE 2
| Mode of intensifying | Chemical sensitization of conventional S-Au | Chemical sensitization of barium chlorofluoride |
| Sensitivity of light | 75 | 200 |
| Fog mist | 0.08 | 0.08 |
| Coefficient of contrast | 0.65 | 0.55 |
The data in the table show: chlorine fluoride of barium (BaFCl: Eu)2+) Compared with the conventional chemical sensitization of sulfur and gold, the chemical sensitization of the silver halide emulsion after chemical sensitization can improve the sensitivity of the emulsion by about 2 times, fog is not increased, and the contrast coefficient is slightly reduced.
Example 3
(1) Firstly, stirring and dispersing 12 g of barium bromofluoride powder in 200 ml of 7 mass percent gelatin aqueous solution, and then carrying out ultrasonic treatment at normal temperature to uniformly disperse barium bromofluoride particles in the gelatin aqueous solution; wherein the mass percentage concentration of the barium bromofluoride in the gelatin water solution is 6 percent.
(2) Uniformly dispersed barium bromofluoride (BaBrF: Eu)2+) Pouring the aqueous solution of gelatin into a ball milling tank for ball milling, and using 100 gelatin500 pieces ofOf zirconia pelletsBall milling at 400 rpm for 25 hr to obtain gelatin water solution containing barium bromofluoride with diameter of about 7 micron and narrow particle size distribution;
(3) at 52 ℃, adding 10 ml of barium bromofluoride gelatin aqueous solution which is obtained after ball milling and has the diameter of about 7 microns and narrow particle size distribution into 100 g of spherical silver bromoiodide emulsion, wherein the adding amount is 1 multiplied by 10 according to each mol of silver in the silver halide emulsion-5After the maturation time was 60 minutes in terms of the molar barium bromofluoride, smear, exposure, development and fixation processing and optical density measurement were performed under a dark room condition, and the following sensitivity data were obtained. The data pair ratio of the method of this example and the conventional chemical sensitization method of S-Au is shown in Table 3.
TABLE 3
| Mode of intensifying | Chemical sensitization of conventional S-Au | Chemical sensitization of barium bromofluoride |
| Sensitivity of light | 75 | 220 |
| Fog mist | 0.08 | 0.08 |
| Coefficient of contrast | 0.65 | 0.53 |
The data in the table show: by bromine fluorineBarium (BaBrF: Eu)2+) Compared with the conventional chemical sensitization of the sulfur and gold, the chemical sensitization of the silver halide emulsion after chemical sensitization can improve the sensitivity of the emulsion by 2 times, fog is not increased, and the contrast coefficient is slightly reduced.
Example 4
(1) Firstly, stirring and dispersing 16 g of barium iodofluoride powder in 200 ml of 7 mass percent gelatin aqueous solution, and then carrying out ultrasonic treatment at normal temperature to uniformly disperse barium iodofluoride particles in the gelatin aqueous solution; wherein the mass percentage concentration of the iodine barium fluoride in the gelatin water solution is 8 percent.
(2) Pouring the uniformly dispersed barium iodide and barium fluoride gelatin aqueous solution into a ball milling tank for ball milling, and utilizing 100 pieces of water500 pieces ofThe zirconia balls are ball-milled at the rotating speed of 500 revolutions per minute for 30 hours to obtain gelatin aqueous solution containing barium iodofluoride with the diameter of about 4 microns and narrow particle size distribution;
(3) at 55 ℃, adding 10 ml of barium iodofluoride gelatin aqueous solution which is obtained after ball milling and has the diameter of about 4 microns and narrow particle size distribution into 100 g of T-shaped silver bromide emulsion, wherein the adding amount is 1 multiplied by 10 according to each mol of silver in the silver bromide emulsion-5After the maturation time was 60 minutes by the calculation of the molar iodine barium fluoride, smear, exposure, development and fixation processing and optical density measurement were performed under a dark room condition, and the sensitivity data were obtained as follows. The data pair ratios of the method of this example and the conventional chemical sensitization method for S-Au are shown in Table 4.
TABLE 4
| Mode of intensifying | Chemical sensitization of conventional S-Au | Chemical sensitization of barium iodide fluoride |
| Sensitivity of light | 75 | 240 |
| Fog mist | 0.08 | 0.08 |
| Coefficient of contrast | 0.65 | 0.50 |
The data in the table show: iodine barium fluoride (BaFI: Eu)2+) Compared with the conventional chemical sensitization of sulfur and gold, the chemical sensitization of the silver halide emulsion after chemical sensitization can improve the sensitivity of the emulsion by more than 2 times, and the fog is not increased. The contrast ratio is slightly reduced.
Example 5
(1) Firstly, stirring and dispersing 20 g of barium bromofluoride powder in 200 ml of 7 mass percent gelatin aqueous solution, and then carrying out ultrasonic treatment at normal temperature to uniformly disperse barium bromofluoride particles in the gelatin aqueous solution; wherein the mass percentage concentration of the barium bromofluoride in the gelatin water solution is 10 percent.
(2) Pouring the uniformly dispersed barium bromofluoride gelatin aqueous solution into a ball milling tank for ball milling, and utilizing 100 pieces of the aqueous solution500 pieces ofThe zirconia balls are ball-milled at the rotating speed of 600 revolutions per minute for 30 hours to obtain the bromofluorination with the diameter of about 1 micron and narrow particle size distributionAn aqueous gelatin solution of barium;
(3) at 55 ℃, adding 10 ml of barium bromofluoride gelatin aqueous solution which is obtained after ball milling and has the diameter of about 2 microns and narrow particle size distribution into 100 g of cubic silver chloride emulsion, wherein the adding amount is 1 multiplied by 10 according to each mol of silver in the silver bromide emulsion-6The maturation time was 80 minutes calculated from the molar amount of barium bromofluoride, and then smear, exposure, development and fixation processing, and optical density measurement were performed under a dark room condition, and the sensitivity data were obtained as follows. The data pair ratios of the method of this example and the conventional chemical sensitization method for S-Au are shown in Table 5.
TABLE 5
| Mode of intensifying | Chemical sensitization of conventional S-Au | Chemical sensitization of barium bromofluoride |
| Sensitivity of light | 75 | 250 |
| Fog mist | 0.08 | 0.08 |
| Coefficient of contrast | 0.65 | 0.50 |
The data in the table show: barium defluorinated bromide (BaBrF: Eu)2+) Compared with the conventional chemical sensitization of the sulfur and gold, the chemical sensitization of the silver halide emulsion after chemical sensitization can improve the sensitivity of the emulsionMore than 2 times higher and the fog is not increased. The contrast ratio is slightly reduced.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (8)
1. A method of chemically sensitizing a silver halide emulsion, characterized by: adding the gelatin solution containing the halogenated barium fluoride particles after ball milling into the silver halide emulsion at the constant temperature of 45-55 ℃, wherein the adding amount is 1 multiplied by 10 according to the addition amount of each mol of silver in the silver halide emulsion-3～1×10-6Stirring for 20-80 minutes for maturation according to the molar calculation of the halogenated barium fluoride, and then quickly freezing and storing;
wherein the particle size range of the barium halofluoride particles in the gelatin solution containing the barium halofluoride particles after ball milling is 1.0-10.0 microns.
2. The method for chemically sensitizing silver halide emulsions according to claim 1, wherein said ball-milled gelatin solution containing barium halofluoride particles is prepared by:
1) uniformly dispersing the barium halofluoride powder in a gelatin aqueous solution and carrying out ultrasonic treatment;
2) and pouring the uniformly dispersed barium fluoride halide gelatin aqueous solution into a ball milling tank for ball milling to obtain the gelatin solution containing barium fluoride halide particles.
3. A method of chemically sensitizing silver halide emulsions according to claim 2, wherein: in the step 1), the mass percentage concentration of the barium halofluoride in the gelatin water solution is 1-10%.
4. A method of chemically sensitizing silver halide emulsions according to claim 2, wherein: in the step 1), the mass percentage concentration of the gelatin aqueous solution is 1-6%.
5. A method of chemically sensitizing silver halide emulsions according to claim 2, wherein: in the step 2), the ball milling speed is 200-600 r/min, and the ball milling time is 15-30 hours.
6. A method of chemically sensitizing silver halide emulsions according to claim 1 or 2, characterized in that: the halogenated barium fluoride is BaFX: eu (Eu)2+Wherein X is one of Cl, Br and I.
7. A method of chemically sensitizing silver halide emulsions according to claim 1, wherein: the silver halide morphology in the silver halide emulsion is one or more of cubic, octahedral, spherical and T-particle.
8. A method of chemically sensitizing silver halide emulsions according to claim 1, wherein: the silver halide in the silver halide emulsion is one or more of silver chloride, silver bromide, silver bromoiodide, silver chlorobromide and silver chloroiodide.
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| JP2000275771A (en) * | 1999-03-24 | 2000-10-06 | Fuji Photo Film Co Ltd | Silver halide photographic emulsion and photosensitive material containing the same, and image forming method by using it |
| US6682868B1 (en) * | 2003-03-26 | 2004-01-27 | Eastman Kodak Company | Radiographic imaging assembly with blue-sensitive film |
| CN101434841A (en) * | 2008-12-18 | 2009-05-20 | 北京交通大学 | Functional material for X ray image storage and preparation thereof |
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| JP2000275771A (en) * | 1999-03-24 | 2000-10-06 | Fuji Photo Film Co Ltd | Silver halide photographic emulsion and photosensitive material containing the same, and image forming method by using it |
| US6682868B1 (en) * | 2003-03-26 | 2004-01-27 | Eastman Kodak Company | Radiographic imaging assembly with blue-sensitive film |
| CN101434841A (en) * | 2008-12-18 | 2009-05-20 | 北京交通大学 | Functional material for X ray image storage and preparation thereof |
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