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Compatibility of high density polyethylene grades with bioethanol-gasoline blends and biodiesel
(2012)
Compatibility of high density polyethylene grades with bioehanol-gasoline blends and biodiesel
(2012)
Biofuels represent an important renewable fuel alternative to petroleum-derived transport fuels. Materials compatibility is a major concern whenever the fuel composition is changed. The aim of this work is to study the interaction of the elastomers: FKM, EPDM, CR, CSM, NBR, IIR, VMQ and FVMQ and biofuels such as biodiesel (FAME), E85 (fuel with 85% ethanol) and B10 (heating oil with 10% biodiesel). Exposure tests were performed with test specimens at 40°C (104°F) and 70°C (158°F) for 84 days to document the changes in mass, volume and tensile properties according to ISO 1817. The exposure tests in E85 showed that the weight gain caused by swelling was in the range up to 12%. The lowest decrease in the tensile properties was determined for FKM, VMQ and IIR. The weight gain of the elastomers in biodiesel varied between 10% (FKM) and 126% (CSM) and the loss of tensile strength between 16% (FKM) and 100% (CSM) at 70°C (158°F). FKM and FVMQ absorbed much less B10 and swelled less. NBR, EPDM, CR, CSM, IIR and VMQ were not resistant to B10 at all as the decrease in the tensile properties was significantly over 50%. Among all of the elastomers FKM showed high compatibility with these biofuels up to 70°C (158°F).
The objective of this research was to determine the resistance of frequently used sealing materials such as EPDM, FKM, FVMQ, CR, CSM, IIR, NBR, PA, PUR and VMQ in aged biodiesel and heating oil B10 with 10 % biodiesel.
The mass, tensile strength, breaking elongation and Shore hardnesses of the test specimens were determined before and after exposure in non-aged, one-year, two-year, three-year and four-year aged biodiesel and B10 at 20 °C, 40 °C and 70 °C.
A threshold for the reduction in tensile properties and Shore hardness is not set in the international standards. Therefore, a threshold of 15 % was set for the evaluation of the compatibility. The decrease in tensile properties and Shore hardness increased with the age and the temperature of the biodiesel and the heating oil.
The age of the biodiesel was not relevant for the sealing materials CR, CSM, EPDM, IIR and NBR, which were generally not resistant to biodiesel and B10. FKM and PA showed high compatibility in non-aged and aged biodiesel. FVMQ and PA could be evaluated as resistant in non-aged and aged B10 at 20°C and 40°C, whereas FKM was resistant up to 70°C despite of the age of B10.
The objective of this research was to determine the resistance of frequently used sealing materials such as EPDM, FKM, FVMQ, CR, CSM, IIR, NBR, PA, PUR and VMQ in aged biodiesel and heating oil B10 with 10 % biodiesel.
The mass, tensile strength, breaking elongation and Shore hardnesses of the test specimens were determined before and after exposure in non-aged, one-year, two-year, three-year and four-year aged biodiesel and B10 at 20 °C, 40 °C and 70 °C.
A threshold for the reduction in tensile properties and Shore hardness is not set in the international standards. Therefore, a threshold of 15 % was set for the evaluation of the compatibility. The decrease in tensile properties and Shore hardness increased with the age and the temperature of the biodiesel and the heating oil.
The age of the biodiesel was not relevant for the sealing materials CR, CSM, EPDM, IIR and NBR, which were generally not resistant to biodiesel and B10. FKM and PA showed high compatibility in non-aged and aged biodiesel. FVMQ and PA could be evaluated as resistant in non-aged and aged B10 at 20°C and 40°C, whereas FKM was resistant up to 70°C despite of the age of B10.
The notched impact strength at -30 °C is one of the selected properties, together with the corresponding test method and tolerances, for a comparison of polyethylene grades of one design type in the procedural rule on suitability proof for alternative plastic resins used for packagings and intermediate bulk containers (IBCs) for the transport of dangerous goods.
The marginal drop heights determined with the drop test at -18 °C after pre-storage of the test samples with 55 % nitric acid at 40 °C only partly related to the notched impact strength at -30 °C. The Charpy method is only suitable for classifying the grade in relation to toughness behavior and using this classification for comparison with other grades. Notched impact strength can provide a qualitative indication if the test samples fail under shock forces.
Conditioning the design types with 55 % nitric acid for 21 days at 40 °C causes an increase in the marginal drop heights of the design types in drop tests at -18 °C when compared with design types without pre-storage. Post-crosslinking of the grades increases stiffness because of the acidic influence.
Resistance to stress cracking by wetting solution is one of the selected properties together with the corresponding test method FNCT and tolerances for a comparison of polyethylene grades of one design type in the procedural rule on suitability proof for alternative plastic resins used for packagings and intermediate bulk Containers (IBCs) for the transport of dangerous goods.
The environmental stress crack resistance determined by Full Notch Creep Test (FNCT) represents the impacts from the stacking tests at 40 °C performed with Standard liquid wetting solution (without pre-storage) and with normal butyl acetate saturated wetting solution (pre-storage with normal butyl acetate). Environmental stress crack resistance determined with FNCT for the polyethylene grades was related to the times to failure of different jerrican samples made of these grades in stacking tests with 5 % wetting solution and a n-butyl acetate saturated wetting solution (pre-storage with n-butyl acetate) at 40 °C. The FNCT is suitable for comparison of polyethylene grades in relation to environmental stress crack resistance independent of their use as drum, IBC or jerrican material. The stiffness of polyethylene grades should be taken into account to the comparison as jerricans are not only chemically but also mechanically stressed.
Technically high-quality hollow articles made of polyethylene have proved many times their value as dangerous goods packagings. Design type tests according to the international regulations for the transport of dangerous goods - drop test, stacking test, hydraulic pressure test and leakproofness test must be performed for every design type and manufacturer. The properties melt flow rate (MFR), relative density (D), low temperature notched Impact strength (N.I.S.) at -30 °C, environmental stress crack resistance (FNCT) and resistance to oxidative degradation Ox by nitric acid (determined by the increase of MFR) have been selected together with the corresponding test methods and tolerances for a comparison of polyethylene grades of one design type in the procedural rule on suitability proof for alternative plastic resins used for dangerous goods packagings and intermediate bulk containers (IBCs) – EN 15507. We wanted to proof the practical relevance of this standard by comparing the relationship between the results of the FNCT and the times to failure of design types in stacking tests with wetting solution and normal butyl acetate saturated wetting solution.
Resistance to stress cracking by wetting solution is one of the selected properties together with the corresponding test method FNCT and tolerances for a comparison of polyethylene grades of one design type in the procedural rule on suitability proof for alternative plastic resins used for packagings and intermediate bulk containers (IBCs) for the transport of dangerous goods.
The environmental stress crack resistance determined by Full Notch Creep Test (FNCT) represents the impacts from the stacking tests at 40 °C performed with standard liquid wetting solution (without pre-storage) and with normal butyl acetate saturated wetting solution (pre-storage with normal butyl acetate).
Environmental stress crack resistance determined with FNCT for the polyethylene grades was related to the times to failure of different jerrican samples made of these grades in stacking tests with 5% wetting solution and a n-butyl acetate saturated wetting solution (pre-storage with n-butyl acetate) at 40 °C. The FNCT is suitable for comparison of polyethylene grades in relation to environmental stress crack resistance independent of their use as drum, IBC or jerrican material. The stiffness of polyethylene grades should be taken into account to the comparison as jerricans are not only chemically but also mechanically stressed.
More than 400 Mt of dangerous materials are transported in Germany every year, of which 150 Mt are by road. Tank containers, tank vehicles and rail tank cars are used for the carriage of dangerous goods in large quantities. Data on the operating life of tanks are only available, in practice, to a minor degree. They are only partly published, mainly after accidents.
The BAM-List - Requirements for Tanks for the Carriage of Dangerous Goods, which has compatibility evaluations of metallic and polymeric materials, has been the basis for substance-related prototype approvals for tank containers and portable tanks designed for the carriage of dangerous goods by the BAM since publication of the first edition in 1989. These data are also used for the approval of rail tank cars and road tank cars and are used as a source of knowledge not only in Germany but also worldwide.
Tank leakages caused by tanks or rail tank cars being made of tank and sealing materials which are not resistant to the fill goods are avoided by using the material resistance data of the BAM.
Corrosion damage is among the main causes of damage. Uniform and non-uniform area corrosion without mechanical stress in aqueous substances is one of the most frequent types of corrosion during the transport of chemicals in tanks. Much damage by pitting corrosion occurs during the transport of substances containing chlorides or substances which separate chloride ions in the presence of moisture.
Operational stresses are caused by the effects of both the road and the dangerous goods being transported. Mechanical damage often results from long-term overstressing and occurs after longer operating times.
Operational failures cause damage which may appear during the service of tank containers, road tank cars or rail tank cars. The damage results from the inattention of employees when opening and closing the valves. Traffic accidents also cause damage to tanks and frames.
Many cases of damage are due to weld area cracks resulting from four basic errors in construction, material, manufacturing and operation. Manufacturing errors can be undetected and the starting point of cracks which only grow under service conditions.
Manufacturing errors result from variations in measurement and design, fittings, state of surface (hardness, abrasiveness) and mechanical surface damage (scratches, cracks). Incorrectly welded joints and errors during mechanical deformation are typical mistakes when installing the component parts. Variations in the wall thickness or combinations of different materials lead to manufacturing errors too. A lot of tanks are not used for the transport of dangerous goods before the end of their service life as they do not fulfil the revised technical safety requirements in the Dangerous Goods Regulations.
Predictions in the BAM-List based on literature data and corrosion test results are reflected in the service (operating) life. Rail tank cars made of carbon steel, for example, which are mainly used for the transport of petroleum products, can achieve a service life of 40 – 50 y.
Rail tank cars produced of austenitic CrNi- or CrNiMo-steel can reach an operating life of at least 30 y, whereby the corrosiveness of the transport substances plays an important role.
The notched impact strength at -30 °C is one of the selected properties, together with the corresponding test method and tolerances, for a comparison of polyethylene grades of one design type in the procedural rule on suitability proof for alternative plastic resins used for packagings and intermediate bulk containers (IBCs) for the transport of dangerous goods.
The marginal drop heights determined with the drop test at -18 °C after pre-storage of the test samples with 55 % nitric acid at 40 °C only partly related to the notched impact strength at -30 °C. The Charpy method is only suitable for classifying the grade in relation to toughness behavior and using this classification for comparison with other grades. Notched impact strength can provide a qualitative indication if the test samples fail under shock forces.
Conditioning the design types with 55 % nitric acid for 21 days at 40 °C causes an increase in the marginal drop heights of the design types in drop tests at -18 °C when compared with design types without pre-storage. Post-crosslinking of the grades increases stiffness because of the acidic influence.
The material parameters melt flow rate MFR, density D, notched impact strength N.I.S. at -30 °C, stress crack resistance FNCT and resistance to oxidative degradation Ox (determined by the increase of MFR) have been selected for a comparison of polyethylene grades for one design type in the “European Standard EN 15507 - Transport packaging for dangerous goods - Comparative material testing of polyethylene grades”. The parameters have a systematic relationship with design type tests. The notched impact strength at -30 °C and the resistance to oxidative degradation of polyethylene grades determined with test specimens of compression moulded sheets are directly comparable with drop tests at -18 °C of design types produced of these grades after pre-storage with 55 % nitric acid for 21 days at 40 °C. The impact of the pre-storage time of jerricans with 55 % nitric acid at 40 °C and 23 °C on the marginal drop heights in drop tests at -18 °C, on the MFR and on the tensile properties tensile strength, breaking elongation and the elastic modulus were investigated. Packaging design types (jerricans) made of three polyethylene grades from different producers were pre-stored with 55 % nitric acid for 21,42 and 84 days at 40 °C as well as for six months at 23 °C. The MFR and tensile properties of test specimens taken from the design type side walls as well as the marginal drop heights of the jerricans in drop tests at -18 °C were determined.
The values of the notched impact strength at -30 °C of polyethylene grades are not comparable with the marginal drop heights determined in drop tests at -18 °C. The oxidative damaging impact of nitric acid has a greater effect on the grade with lower resistance to oxidative degradation by reducing more significantly the marginal drop heights with increasing pre-storage time.
Pre-damage with 55 % nitric acid for 21 days at 40 °C, as recommended in ISO 16101 and EN 15507 caused an increase in the marginal drop heights of most design types in drop tests when compared with design types without pre-damage. The test results demonstrated clearly that pre-storage of the jerricans for six months at 23 °C caused a higher increase in the MFR and lower marginal drop heights of the jerricans in drop tests at -18 °C compared with pre-storage of the jerricans for 21 days at40 °C.
The mechanical properties change as a result of diffusion of nitric acid into the polyethylene grades and the reaction of the nitric acid with the polymers. The percentage decrease and increase in the tensile strength, breaking elongation and elasticity modulus of test specimens taken from the design type side walls after different pre-storage times were only partly comparable with the marginal drop heights in drop tests at -18 °C.
The material parameters melt flow rate (MFR), density (D), notched impact strength (NIS) at –30°C, stress crack resistance [determined with the Full Notch Creep Test (FNCT)] and resistance to oxidative degradation (Ox) have been selected for a comparison of polyethylene grades in the European standard EN 15507. These parameters have a relationship with design type tests of packagings for the transport of dangerous goods.
This paper presents the results of additional investigations to determine the impact of the pre-storage time of jerricans with 55% nitric acid at 40°C and 23°C on the marginal drop heights in drop tests at –18°C, on the MFR and on the tensile properties. Jerricans made of different polyethylene grades were pre-stored with 55% nitric acid for 21, 42 and 84 days at 40°C and for six months at 23°C.
The tests showed that the NIS values at –30°C of polyethylene grades were not comparable with marginal drop heights determined in drop tests at –18°C.
Pre-damage with 55% nitric acid for 21 days at 40°C led to an increase in the marginal drop heights of the jerricans. Altering the test regulations by increasing pre-storage time with 55% nitric acid to 42 days would be an alternative.
The test results demonstrated clearly that pre-storage of the jerricans for six months at 23°C caused a higher increase in the MFR and lower marginal drop heights for the jerricans when compared with pre-stored jerricans for 21 days at 40°C.