Kaplama ve polimerlerde kullanılan alüminyum ve antimon içerikli alev geciktricilerin tayini
Determination of aluminum and antimony containing flame retardants used in coatings and polymers
Yazar: MURAT TURAL
Danışman: PROF. DR. MUSTAFA ŞAHİN DÜNDAR
Sakarya Üniversitesi / Fen Bilimleri Enstitüsü / Yangın ve Yangın Güvenliği Anabilim Dalı
Derece: Yüksek Lisans, 2023
Konu: Kimya = Chemistry ; Kimya Mühendisliği = Chemical Engineering ; Mühendislik Bilimleri = Engineering Sciences

Özet:
Polimer ve kaplama endüstrisinde üretilen ve kullanılan hammadde ve ürünlerin gündelik yaşamımızda çok sık yer aldıklarını görmekteyiz. Kullanım alanlarından bazıları; otomotiv, ambalaj, deri, branda, kauçuk ürünleri, zemin kaplamaları, çadır, halı arkaları gibi plastik ürünleridir. Hayatımızda bu kadar kadar geniş yer almaları bazı riskleri de beraberinde getirmektedir. Bunların en başında yangın ve sağlık konusu gelmektedir. 
Yangın güvenliğinde de bu polimer ve kaplama ürünlerine; alev geciktirici özellikleri olması sebebiyle antimon ve alüminyum elementleri çok sık kullanılmaktadır. Bu çalışmada; içerisinde alüminyum ve antimon elementleri bulunan Polivinil klorür (PVC) polimeri olan kaplama ürünlerinden olan suni deri, branda ve çadır numuneleri üzerinde deneyler gerçekleştirilmiştir.  
Yangın güvenliğinde etkili olan bu metallerin kullanımlarının sağlık açısından etkilerinin incelenmesi amacıyla daha duyarlı ve maliyet açısından ucuz olan bulutlanma noktası ekstaraksiyonu (CPE) metoduyla tayinleri gerçekleştirilmiştir. 
Bu çalışmada alev geciktirici olarak kullanılan Alüminyum (Al) ve Antimon (Sb) içerikli polimer ve kaplama numunelerinde, indüktif eşleşmiş plazma optik emisyon spektrometresi (ICP-OES) cihazı kullanılarak ve bulutlanma noktası ekstraksiyonu yöntemi uygulanarak Alüminyum (Al) ve Antimon (Sb) metallerinin tayini gerçekleştirilmiştir. Yüzey aktif madde  (1,1,3,3-Tetrametilbutil) fenil-polietilen glikol (Triton X-114) ve kompleksleştirici madde olarak da 1,5-difeniltiyokarbazon (ditizon) çalışmada kullanılmıştır. Bu çalışmada optimum pH değeri 6, optimum ligand derişimi 1 mmol/L, optimum yüzey aktif madde derişimi 1,5 mmol/L, optimum inkübasyon sıcaklığı 60 oC ve optimum inkübasyon süresi de 45 dakika değerlerine deneysel çalışmalar sonucunda ulaşılmıştır. Sonrasında Na+,  K+,  NO3-, SO4-2, Ca+2, Mg+2, Cl-, CH3COO-  ortak iyonlarının  etkisi sonucu en uygun aralıklar bulunmuştur. Analitik parametrelerden gözlenebilme sınır değerleri (LOD) Al için 0,018 µg/L Sb için 0,107 µg/L ölçülmüştür. Bağıl standart sapma değerleri yüzde olarak Al için  5,52 ve Sb için  5,96 olarak bulunmuştur. Son olarak PVC suni deri, branda ve çadır  örneklerine de  bulutlanma noktası ekstrasiyonu metodu ve elde edilen optimum koşullar uygulanarak Al ve Sb metalleri için geri kazanım oranları deri kaplama numunesinde yüzde olarak Al için  % 103,2 ve Sb için % 96,7 PVC kaplama numunesinde Al için  % 103,4 ve Sb için % 98,2 PVC kaplama branda-çadır numunesinde Al için  % 95,1 ve Sb için % 95,3 olarak bulunmuştur.

Abstract:
Polymer and coating materials; It is seen that they are consumed as raw materials in many industries or as final products in many areas in daily life. For example; flooring industry, construction, furniture, tarpaulin, tent, artificial leather, packaging, floor covering etc. For this reason, with their use in many areas, the issue of fire safety becomes important. For fire safety, some substances are used as additives to these materials during the production phase or later. The main task of these substances in fire safety is to stop the progress and spread of fire. The materials used at this stage are called flame retardant additives.
Flame retardant additives are divided into four classes: halogen-based, phosphate-based, inorganic-based and nitrogen-based. Some of the usage areas of flame retardants are; sectors such as automotive, paper industry, packaging, textile, leather, tarpaulin, rubber products, floor coverings, tent carpet backing. Especially in the polymer industry; It is used directly or by adding to many polymers such as PVC, olefins, polypropylene, polyester, epoxy resins, polyurethane foam.
Aluminum hydroxide and antimony trioxide types, which are inorganic based flame retardant types, are used in the samples we used in this study and in many products as flame retardants in the field of fire safety. Polyvinyl chloride (PVC) polymer is used in these two products. PVC polymer is used in many sectors and industries in various fields. Some of those; construction, coating, packaging, artificial leather, etc. In this study, three different Polyvinyl chloride (PVC) based artificial leather, tarpaulin and tent samples were used, in which flame retardants containing antimony trioxide and aluminum hydroxide were used. Samples were requested from different companies.
The antimony and aluminum metals, which can be harmful to health during combustion of the products in which these flame retardants are used, can be separated from their environment with a simple method, and it can be easily carried out with the cloud point extraction (CPE) method. The cloud point extraction method is one of the advantages of choosing this method, because the solvents used are not toxic, but also sensitive and cost-effective. In order to examine the health effects of the use of aluminum hydroxide and antimony trioxide type flame retardants, which are effective in fire safety, it is aimed to determine the antimony and aluminum metals in the samples with the more sensitive and cost-effective cloud point extraction (CPE) method.
Cloud point extraction is used in many fields. Some of those; enzymes, hormones, vitamins, etc. we can say the separation of biological samples and the determination and enrichment of environmental samples. The basis of the cloud point extraction (CPE) process is that the solubility of the nonionic surfactant decreases and becomes cloudy, inversely proportional to the increase in temperature. In phase separation, which occurs at cloud point temperature, the surfactant-rich phase becomes stable in phasing when the metal forms a complex with the ligand. In this case, when phase separation occurs, the metal-ligand complex is separated from each other in the surfactant-rich phase. The centrifuged samples are kept in ice for a while so that the phases can be evident.
Inductively coupled plasma optical emission spectrometry (ICP-OES) device was used in the reading and analysis part for the samples applied cloud point extraction method. The ICP-OES device is very effective in this kind of work for analysis. Even though it is more expensive to analyze with the ICP-OES device than with the AAS device, it is suitable for the simultaneous determination of metal ions.
Inductively Coupled Argon Plasma-Optical Emission Spectrometer is a method used in the analysis of dissolved elements in aqueous solutions. The working principle of the device is based on the excitation of the sample by the argon plasma, which is reached to high temperatures (6000-10000 ºK) by electromagnetic induction, and the determination of the excited elements according to the specific wavelengths they emit and the intensity of emission.
In this way, qualitative and quantitative analyzes of many elements are made. Thanks to the detector system, which includes bidirectional imager optics (axial and radial), analyzes can be made in a wide linear range and with ppb-ppm sensitivity. Analysis is carried out on samples brought dissolved and filtered in ICP-OES. Analysis results are optionally given as mg/kg, mg/L or %.
In this study, with the ICP-OES device, the determination of Al and Sb metal ions in 3 different samples could be easily carried out simultaneously.
Although there are many methods for the extraction of metals in recent years, the cloud point extraction method has still not lost its value and its use is included in many studies. The most important goals to be achieved in the studies in which this method is applied are to optimize the variables such as surfactant and its concentration, complexing agent and its concentration, pH of the environment and incubation time and temperature, to bring the recovery rates of metal ions to the highest values. In the study, the optimization of these values was carried out separately for each variable to bring them to the most appropriate values. The effects of common ions were also investigated.
In this study, the metals to be extracted were chelated with 1,5-diphenylthiocarbazone (dithizone) as a hydrophobic complexing agent for aluminum and antimony, and preconcentration was carried out with the surfactant Triton-X114 by settling in the micelle.
Ambient pH is one of the first variables to be investigated in the preconcentration process. In the study, it was observed that 1,5-diphenylthiocarbazone (dithizone) reached higher extraction efficiency values in basic media. It can be said that better dissolution of 1,5-diphenylthiocarbazone (dithizone) in basic media causes an increase in extraction efficiency. In this case, the reason why the pH 6 value is chosen as the most suitable is that it is undesirable in this case as precipitation in hydroxide structure may occur due to the very basic environment of the precondensed metal ion. It was observed that the highest recovery rate was reached after the trials carried out between pH=6 and 2-10 values.
Complexing agent concentration is another important variable to be investigated for extraction efficiency. Due to the fact that the metal ions to be extracted cannot form complexes under conditions where the complexing agent is low in the environment, they are found as a precipitate in the solution environment and cause a decrease in the recovery rate. Surfactant micelles cannot capture these complexes because the complexes formed by the increase of the complexing agent in the medium pass into the aqueous phase. For these reasons, the concentration of the complexing agent in the environment should be in the most appropriate way and the recovery rate should be the highest value. In the study, the most suitable sequestrant concentration for 1,5-diphenylthiocarbazone (dithizone) was found to be 1x10-3 M.
Surfactant concentration is also one of the important variables studied third. Triton-X114 surfactant, which was tested at different concentrations in the study, gave the highest recovery rate at a concentration of 1.5% (v/v). The phase rich in surfactant was diluted with 2M HNO3 solution and the device was read.
Reaction time and temperature are other important variables examined in the study. Complex structures may deteriorate at high temperatures, otherwise micelle formation is not observed as the surfactant cannot reach the critical temperature with the decrease in temperature. In this study, it was observed that the highest recovery rates were achieved at the temperature value of 60 oC, and the extraction efficiency decreased at temperatures below and above this value. One of the factors affecting the extraction efficiency is the reaction time. In the study conducted for the reaction time, it was observed that the micelle formation of the samples reached the highest recovery rates in 45 minutes.
The common ion effect study was also done to see how different ions that may be present in the environment affect the extraction efficiency. As can be seen from the results, many different cations and anions have a very low effect on the recovery percentages of the analyte solution, even if it is more than 2500 times in the environment. On the contrary, it was observed that cations, which were added to the medium in smaller amounts and affected the extraction efficiency, formed a complex with 1,5-diphenylthiocarbazone (dithizone), thus decreasing the extraction efficiency even a little.
The accuracy of the method was tested by applying the cloud point extraction method used in the study to PVC-based artificial leather coating, tarpaulin and tent samples. In the study, the applicability of the method to real samples was proved by providing recovery of PVC-based artificial leather coating, tarpaulin and tent samples by cloud point extraction method.
In this study, the determination of Al and Sb metals, which are used as flame retardants in polymers, was achieved by using the cloud point extraction method developed with inductively coupled plasma optical emiston spectrometry (USN-ICP-OES) combined with an ultrasonic nebulizer. 1,5-diphenylthiocarbazone (dithizone) hydrophobic sequestrant and (1,1,3,3-Tetramethylbutyl) phenyl-polyethylene glycol (Triton X-114) were used as surfactant. In the study, the most appropriate data were obtained as optimum pH value 6, optimum ligand concentration 1 mmol/L, optimum surfactant concentration 1.5 mmol/L, optimum incubation temperature 60 oC and optimum incubation time 45 minutes. Then, the most suitable ranges were found as a result of the effect of Na+, K+, NO3-, SO4-2, Ca+2, Mg+2, Cl-, CH3COO- common ions. Observable limit values (LOD) of the analytical parameters were also found to be 0.018 µg / L  for Al and 0.107 µg / L  for Sb. Relative standard deviation values were found to be 5.52% for Al and 5.96% for Sb as a percentage. Finally, by applying the cloud point extraction method and the obtained optimum conditions to PVC imitation leather, tarpaulin and tent samples, the recovery rates for Al and Sb metals are 103.2% for Al and 96.7% for Sb, as a percentage for leather coating sample, PVC coating sample It was found that 103.4% for Al and 98.2% for Sb in percentage, 95.1% for Al and 95.3% for Sb in percentage of PVC coated tarpaulin-tent sample