مطالعه ساختاری و فرایند تخریب یک نمونه فیلم سینماتوگراف پایه نیترات سلولز

فیلم های سینمایی بخش مهمی از میراث فرهنگی تاریخی و اسناد تصویری تاریخ ایران را تشکیل می دهند. تغییرات ساختاری در فیلم ها، با توجه به عوامل موثر بر آن ها در طول زمان منجر به تخریب تصویر می شود. مطالعات ساختاری و فرایند تخریب کمک شایانی به ارائه راهکار های حفاظتی و مرمتی در این گونه آثار می کند. در این پژوهش یک نمونه فیلم سینماتوگراف موردمطالعه قرار گرفت. نتایج حاصل از آزمایش های atr-ftir، تصاویر میکروسکوپ نوری و تصاویر sem در نمونه فیلم نشان داد که تکنیک ساخت نمونه ژلاتین و هالید نقره بر روی پایه پلاستیک نیترات سلولز است و تخریب در لایه تصویر ناشی از آزاد شدن گاز no2 در پایه فیلم است. گاز های آرشیوی (پراکسیدها) ناشی از شرایط نامناسب محیطی و استفاده از مواد نامناسب در نگهداری نمونه موردپژوهش باعث اکسید شدن نقره در لایه تصویر، مهاجرت آن به سطح فیلم و منجر به عارضه تاول های اکسایش کاهش شده است. نتایج حاصل از آنالیز sem/eds تاول های اکسایش-کاهش در سطح فیلم نشان دهنده تخریب یون های نقره در لایه تصویر است.

Technical Study and Mechanism of Deterioration in a Nitrocellulose based Film

Nitrocellulose based film negatives make an important part of the cinematic work. In Iran, these films are also important since they are parts of cultural, historical and artistic heritages. Therefore, such works need to proper care and preservation. The decomposition process of these films occurs due to the inherent deterioration of nitrocellulose as well as the presence of environmental factors such as heat, light and humidity. Nitrocellulose film base decomposition can be very rapid and is generally categorized in five progressive stages; 1. The negatives begin to become yellowishbrown and NO2 gas is released; 2. The film becomes sticky and emits a strong noxious odor; 3. The film changes to an amber color material and the image begins to fade; 4. The negative becomes soft and can weld to adjacent negatives, enclosures and photographs; and 5. The negative decomposes into a brownish acid powder. Technical study and mechanism of deterioration of cinematograph negatives can help to provide better methods of conservation and restoration of this works. In this study, a cinematographic negative sample was investigated by Fourier Transform Infrared spectroscopy Attenuated Total Reflectance (FTIRATR), spot tests (diphenylamine test and float test), Scanning Electron Microscopy/Energydispersive Xray spectroscopy (SEM/EDS), optical microscope images and digital loop. The mdash;ONO2, C mdash;O, mdash;OH, C=O groups in the base of the sample and mdash;CH, mdash;CN, mdash;NH, mdash;OH, amide I, and amide II groups in the image layer were identified by FTIRATR spectra. A solution of diphenylamine and sulfuric acid was used to identify the negative base, where it contains 90% of sulfuric acid. The color of the solution turned into a deep blue color upon the immersion of the sample. The sample was also sunk in trichlorethylene solution. Results of FTIRATR analysis, spot tests and cross section images by SEM indicated that the structure of the negative is gelatin and silver halide (image layer) on the nitrocellulose plastic base. The instability of nitrocellulose based cinematograph negative can be attributed mostly to the extremely thermal sensitivity of nitrocellulose. An examination of bond energy implies the oxygennitrogen (O mdash;N 169 kJ; C mdash;C 347 kJ; C mdash;O 360 kJ; C mdash;H 414 kJ) linkages are almost readily cleaved, leading to the formation of volatile nitrogen oxide decomposition products. The degradation in the image layer in the form of brown bobbles, due to release of NO2 gas in the negative base was observed by optical microscope and digital loop images. Redox blemishes also were observed by optical microscope and digital loop images in the shape of yelloworange circles on the surface of the negative. Redoxblemishes were observed for the first time in 1960s on the surface of the microfilms. At first, the problem of redox blemishes was thought to be peculiar to microfilm. But, it was later found to occur on many types of silver photographic materials. Archival gases (peroxides) produced by improper environmental conditions and use of inappropriate materials in the maintenance of the sample cause the oxidation of silver in the image layer, its migration to the surface of the negative and led to the formation of Redox blemishes. The results of the SEM/EDS analysis of Redox blemishes on the negative surface indicate the deterioration of silver ions in the image layer. Humidity also accelerate Redoxblemishes.