Earticle

들기름은 단청, 석조물, 철물 등 문화유산 수리⋅복원에 사용되는 대표적인 전통 도료이다. 본 연구에서는 들기름(생들기름)과 명유 3종을 대상으로 열분해 기체 크로마토그래피법과 감쇠 전반 사 푸리에변화 적외선 분광법으로 경화 및 열화 전후의 성분 변화를 분석하였다. 액상 상태의 들기름 에서는 불포화 지방산인 올레산(oleic acid), 리놀레산(linoleic acid), 리놀렌산(linolenic acid)과 포화 지방산인 팔미트산(palmitic acid), 스테아르산(stearic acid)이 주성분으로 검출되었으며, 명유 시료에 서도 동일한 조성이 확인되었다. 경화가 진행됨에 따라 액상에서는 검출되지 않았던 수베르산 (suberic acid), 아젤라산(azelaic acid), 세바식산(sebacic acid)이 공통적으로 생성되었고, 다가 불포화 지방산인 리놀렌산은 소멸되는 경향을 보였다. 이러한 변화는 C=C와 C=C-H 흡수띠의 소멸을 통해 산화 반응의 진전으로 확인되었다. 목재 기재에 들기름과 명유를 도포한 시편의 경우, 경화 이후에도 들기름류의 특성 성분이 표면에 잔존하였으며, 기본적인 지방산 조성은 경화된 들기름과 유사하였 다. 누적 자외선량이 증가할수록 리놀렌산 및 리놀레산 등 다가 불포화 지방산이 소멸하고, 아젤라산, 팔미트산, 스테아르산이 주요 성분으로 검출되는 열화 특성이 관찰되었다. 본 연구는 들기름류의 경화 및 열화 과정에서 나타나는 주요 화학적 변화를 규명하고, 환경 요인에 따른 성분 변화를 제시 함으로써, 전통 식물성 도료의 과학적 이해와 문화유산 보존 분야의 적용 가능성 평가에 기초자료로 활용될 수 있을 것이다.

Perilla oil is a representative traditional drying oil used for the restoration and conservation of cultural heritage objects such as painted architecture, stone artifacts, and metal works. In this study, compositional changes before and after curing and ageing were analyzed for raw perilla oil and three types of myeong-yu (boiled perilla oil) using pyrolysis-gas chromatography/mass spectrometry(Py-GC/MS) and attenuated total reflection infrared spectroscopy(ATR-FTIR). In the liquid state, the main fatty acids detected were the unsaturated fatty acids oleic acid, linoleic acid, and linolenic acid, and the saturated f atty acids palmitic acid and s tearic acid. A s imilar composition was also observed in the myeong-yu samples. During the hardening process, suberic acid, azelaic acid, and sebacic acid— which were not detected in the liquid state—were commonly identified, while the polyunsaturated fatty acid linolenic acid tended to disappear. These changes indicate the progression of oxidation reactions, as confirmed by the disappearance of C=C and C=C–H absorption bands in the FT-IR spectra. In the wood specimens coated with perilla oil, the components of the oil remained on the surface even after hardening, and their basic fatty acid composition was similar to that of the hardened perilla oil. As the cumulative light exposure increased, polyunsaturated fatty acids such as linolenic and linoleic acids diminished, while azelaic, palmitic, and stearic acids became the predominant components. This study elucidates the characteristic chemical transformations that occur during the curing and degradation of perilla oil-based materials and identifies compositional changes induced by environmental factors. These findings provide fundamental data for advancing the scientific understanding of traditional plant-based coatings and for evaluating their applicability in cultural heritage conservation.

As crimes and criminal methods become more sophisticated, including attempts to conceal evidence, there are cases where corpses are meticulously and thoroughly hidden. One such example is when skeletal remains are discovered within the cement structures that are being demolished for reconstruction or other purpose. However, it is difficult to detect whether a body has been buried within a cement structure prior to its demolition. In this study, animal corpses were buried in commonly used cement mortar, and the gas components generated during decomposition were examined to assess the possibility of using these components as indicator substances for locating burial sites. Among the various components detected during the decomposition of bodies buried in cement materials, dimethyl disulfide and phenol were distinctively identified. These components show promise as indicators for tracking corpses in the early stages of burial, although the influence of components originating from the surrounding environment cannot be ignored after a long period of time.

옻칠은 천연도료로써 기원전 1~2세기부터 한반도에서 사용되었으며 접착제로도 활용되었다. 이러한 접착제로써의 기능은 고문헌과 실제 출토되는 유물에서 찾을 수 있으며, 아교, 밀가루, 어교 등을 혼합하여 사용했다는 사실을 확인할 수 있다. 본 연구는 첨가물을 혼합한 칠의 정성분석을 통하여 칠분석 및 혼합재료에 대한 분석가능성을 확인해보고자 하였다. 첨가물을 혼합한 칠에 대한 정성분석 결과, EGA분석을 통해 옻, 찹쌀풀, 아교의 열분해 온도를 확인하였다. 이를 바탕으로 Py-GC/MS 분석을 통해 생칠 시료의 경우 우루시올 곁사슬(R기)에서 유래된 열분해 산물을 확인하였으며, 찹쌀풀과 아교 각각 글루코오스와 아미노산에서 유래된 물질로 추정되는 성분이 검출되었다. 본 연구를 통해 옻과 첨가물별 최적의 열분해 온도를 확인하였으며, 열분해 산물에 대한 기초 정성분석 값을 제시하였다. 첨가물 혼합 비율별 정성분석을 실시하여 실제 유물에서 관찰되는 칠 접착제 분석 가능성을 확인하였다.

Lacquer has been used as a natural paint or adhesive in Korea since 2nd century B.C. It has been found to have been used as an adhesive as mentioned in old records and as seen in excavated relics, It was also mixed with flour, animal glue, or fish glue to produce lacquer adhesives. Qualitative analysis and evaluation of the applicability of lacquerand additives was performed in this study. The results of EGA analysis for lacquer additives confirmed that the pyrolysis temperature of lacquer, glucose glue, and animal glue. On the basis of this result, raw lacquer sample was checked that pyrolysis product that originated from urushiol side chain (R group). Components originating from glucose and amino acid were detected in glutinous rice paste and animal glue samples. In this study, the optimum pyrolysis temperature for each lacquer and additive mixture was determined from basic qualitative analysis data. By performing the qualitative analysis of each mixture, the applicability of this technique for analyzing real relics was evaluated.

본 연구에서는 Py-GC/MS(Pyrolysis Gas Chromatography Mass Spectroscopy)를 이용하여 단백질섬유(Protein fiber)로 이루어진 15종의 모피를 열분해 분석하였다. 열분해에 의해 생성된 성분들은 열분해 경로(pyrolysis pathway)및 기원(origin)에 따라 단 분자 열분해 화합물과 이 분자 열분해 화합물로 분류하여 변수화하였고 주성분분석(Principal component analysis)으로 통계 처리하여 섬유의 개체식별, 동물 종류에 따른 미세분류 가능성을 알아보았다.

To find the best method to contribute the species of animal hair using analytical pyrolysis, the thermal decomposition fragments of 15 species of animal hair were analysed by Pyrolysis Gas Chromatography Mass Spectroscopy(Py-GC/MS). Then some fragments which originated from mono amino residues and amino residue pairs were arranged as factors to distribute species of fiber and each individual fiber. Principal component analysis was used to verify this method have applicability.

칠기문화재 보존에 옻칠이 사용되지만 근대화로 인해 캐슈칠과 같은 합성도료가 같이 사용되는 추세이다. 보존윤리에서는 문화재 보존 시 동일 재료가 사용되어야 한다고 명시되어있다. 따라서 칠기문화재 보존에는 옻칠과 같은 천연 도료가 사용되어야 한다. 하지만 옻칠과 캐슈칠의 성분이 유사하여 전문가들도 쉽게 구분하지 못하는 실정이다. 본 연구에서는 IR과 Py-GC/MS를 이용하여 이를 분석하고 식별 키워드를 찾고자 하였다. IR 분석 결과 옻칠은 $720cm^{-1}$ 대에서 피크가 확인되었으며 캐슈칠은 $750cm^{-1}$, $720cm^{-1}$, $700cm^{-1}$ 대에서 피크가 확인되었다. Py-GC/MS 결과 두 종류의 시료에서 Benzene과 Phenol계 화합물과 알킬사슬고리에 기인하는 성분이 검출되었다. 하지만, 캐슈칠에서는 Hexanoic acid라는 성분이 검출되었고 옻칠에서는 검출되지 않았다. 이러한 분석방법을 토대로 진정성 있는 칠기문화재 보존처리 및 복원에 활용될 수 있을 것이라 판단된다.

Nowadays, synthetic resin varnish such as cashew nut shell liquid (CNSL) is being used as well as traditional lacquer. The code of ethics states that material must be identical to the original when preserving cultural heritage. Therefore, lacquer should be used. However, problem is that even experts have difficulties differentiating lacquer and CNSL as they have similar components. Therefore, this study was carried out to identify the difference between lacquer and CNSL using IR and Py-GC/MS. As a result of IR, in lacquer, $720cm^{-1}$ peak was detected and in CNSL, $750cm^{-1}$, $720cm^{-1}$ and $700cm^{-1}$ peaks were detected. The results of Py-GC/MS detect benzene compounds and alkyl chains for both varnishes. However, hexanoic acid was detected from CNSL but not lacquer. Using these analytical methods, the differences between lacquer and CNSL can be identified on the scene. This is expected to be applied to the authentic conservation and restoration of lacquerware.

A calibration curve is needed to determine the SBR and BR blend ratio of SBR/BR blend rubber compounds using pyrolysis-gas chromatography/mass chromatography (Py-GC/MS) or Py-GC. In general, a calibration curve is obtained using reference SBR/BR vulcanizates with various blend ratios. In this study, the calibration curves were obtained using reference samples made of rubber solutions and were compared to those plotted using the reference SBR/BR vulcanizates. Calibration curves using variations of 1,3-butadiene/styrene, 4-vinylcyclohexene (VCH)/styrene, 2-phenylpropene (PhP)/butadiene, PhP/VCH, 4-phenylcyclohexene (PhCH)/butadiene, and PhCH/VCH ratios with the BR content were examined for the suitability. We found that the calibration curves obtained using the mixed rubber solution references (1,3-butadiene/styrene and PhP/butadiene) could replace those constructed using the reference SBR/BR vulcanizates. The calibration curves of 1,3-butadiene/styrene and PhP/butadiene obtained using the raw references can be used for the determination of the SBR/BR blend ratios by applying some correction factors.

호박유물의 적절한 보존방안 마련에 필요한 호박의 화학적 분광학적 특성을 Infrared (IR) 분석과 pyrolysis/GC/MS (py/GC/MS) 분석을 통해 조사하였다. 호박 시료는 Baltic, Chiapas, Colombian, Dominican, Fushun, Madagascar 호박 등 6개의 산지에서 총 14종을 확보하였다. 시료의 비파괴적 조사를 위해 IR 분석을 실시하였고, 고분자 구성 성분 조사를 위해 py/GC/MS를 $300^{\circ}C$ 열분해 온도에서 온라인 trimethylsilylation을 통하여 분석하였다. IR 분석에서는 대체적으로 산지에 관계없이 유사한 스펙트럼을 보였으나, 지문영역에서는 Baltic 호박의 경우 Baltic shoulder에 해당하는 $1250cm^{-1}{\sim}1150cm^{-1}$에서 흡수가 나타나는 등 각각의 산지별로 구분이 가능한 차별화된 IR 스펙트럼이 관찰되었다. py/GC/MS 분석에서는 succinic acid, pimaric acid 등 호박의 구성성분으로 알려진 물질들이 검출되었고, Baltic, Chiapas, Fushun 호박의 경우 산지 구분이 가능한 특정성분이 검출되었다. 이러한 결과는 발견 및 발굴 유물에서 호박을 확인하거나, 산지 및 제작기술 추정 등 고고과학적인 해석의 기초 자료로 활용될 수 있을 것으로 기대된다.

Ambers have been used as a gemstone and a religious object since the ancient times and found in several archaeological sites in Korea. To prepare an enhanced conservation measures, we surveyed the chemical and spectroscopic properties of the ambers according to the provenance. Total 14 amber samples were collected from 6 different provenances including Baltic, Chiapas, Colombian, Dominican, Fushun and Madagascar amber. Infrared (IR) spectroscopic analysis was conducted for the non-destructive examination of the amber samples. They were also analyzed with pyrolysis/GC/MS (py/GC/MS) at the pyrolysis temperature of $300^{\circ}C$ with the on-line derivatization to trimethylsilyl ester. Baltic shoulder corresponding to the absorption at $1250cm^{-1}{\sim}1150cm^{-1}$ appeared in the IR spectrum of Baltic amber. IR spectra of the other ambers also showed somewhat distinctive characteristic peaks. In py/GC/MS analysis peaks assignable to succinic acid, dehydroabietic acid and pimaric acid were detected, which are known to be the components of the amber. In the meanwhile, the presence of compounds appearing in certain amber will be applied to differentiate the provenances of amber relics if their fragments are available for the analysis. These results are expected to help the confirmation of archaeological amber relics and archaeometric interpretation of provenances and manufacturing techniques.

The catalytic pyrolysis of cellulose was carried out over SAPO-11 for the first time. Pyrolyzer-gas chromatography/mass spectroscopy was used for the in-situ analysis of the pyrolysis products. The acid sites of SAPO-11 converted most levoglucosan produced from the non-catalytic pyrolysis of cellulose to furans. In particular, the selectivity toward light furans, such as furfural, furan and 2-methyl furan, was high. When the catalyst/cellulose ratio was increased from 1/1 to 3/1 and 5/1, the increase in the quantity of acid sites led to the promotion of deoxygenation and the resultant increase of the contents of light furan compounds. Because furans can be used as basic feedstock materials, the augmentation of the economical value of bio-oil through the catalytic upgrading over SAPO-11 is considerable.

The effect on the hydrolysis resistance properties by the addition of maleic anhydride grafted EMDM (MA-g-EPDM) and PP (MA-g-PP) to a PA66/GF composite was investigated with respect to the mechanical properties, thermal properties, and morphology. The degree of hydrolysis of the PA66/GF composite was measured using py-GC/MS analysis. When compared to the PA66/GFcomposite in MEG/water solution, the composites where MA-g-EPDM and MA-g-PP were added to PA66/GF showed a higher degree of hydrolysis resistance, impact strength, and thermal properties, whereas their tensile strength, tensile modulus, flexural strength and flexural modulus decreased. As immersion time in the solution increases, the rate of tensile strength drop of the MA-g-PP added composite appeared lower than that of the PA66/MA-g-EPDM/GF and PA66/GF composites. The py-GC/MS analysis confirmed the formation of PA66 hydrolysis reaction by products such as carboxylic acid and alkylamine with increasing immersion time.