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Environmental Project no. 744, 2003 Evaluation of Plasticisers for PVC for Medical DevicesContentsForewordIt is experienced that it is extremely complicated to find alternative materials to polyvinylchloride in general and in Medical device applications particularly. In Denmark Medical Devices are pointed out as a field of high priority requiring a particular effort to substitute phthalates as plasticising agents. Medical Devices are a field of high priority, because the phthalates are able to migrate from the plastic, and unwanted biological and environmental properties are suspected. A number of national and international industrial development programmes on Plasticisers alternative to phthalates - particularly di(2-ethylhexyl)-phthalate - have been and are being conducted. In 1998 a Danish/British/Italian Brite-EuRam research project on development, evaluation and validation of Plasticisers for use in flexible PVC Medical device applications was proposed but rejected. However, the Danish Environmental Protection Agency decided to support the first two tasks of this original project. This work is presented in this report. The objective of this project is to select and evaluate non-phthalate Plasticisers for PVC for Medical Devices. The project partners are Maersk Medical A/S, Totax Plastic A/S and Danish Technological Institute, Centre for Plastics Technology. Subsuppliers are Hydro Polymers Limited, Laporte Performance Chemicals UK Ltd. and University of Strathclyde, Bioengineering Unit. From the beginning of the work the working group consisted of Maersk Medical A/S, Totax Plastic A/S, Danish Technological Institute, Papyro-Tex A/S (a subsidiary of Maersk Medical A/S) and Hydro Polymers Limited. The working group was in current contact with Laporte Performance Chemicals, who later on was included in the project group particularly during the collection of information on commercially available Plasticisers and the selection of substances to be included in the test program. Furthermore, the PVC Information Council Denmark (PVC Informationsrådet) has been represented at most of the working group meetings. The below-mentioned experts have worked in the project: Karen Marie Andersen, Papyro-Tex A/S A reference group has been formed with the above mentioned persons and those mentioned below as members: Lea Frimann Hansen, Danish Environmental Protection Agency, chairman Summary and conclusionsOn the basis of a feasibility study of the plasticiser substances and groups of substances that are commercially available on the market today, nine substances were selected for further investigations. PVC compounds plasticised with these selected substances were prepared and tested for a number of properties that were considered as primary selection criteria for Medical applications. Compounding was easy with all the investigated plasticising substances and it was easy to prepare specimens and test samples by injection moulding with all the prepared compounds. An attempt was made to rank the selected and investigated substances in comparison with a reference DEHP plasticised PVC compound. Some have a slightly lower strength value, some have a slightly lower strain at break value, and some have a higher cold flexibility temperature. None of the substances was rejected as potential alternatives to DEHP. However, much more data are needed before DEHP can be seriously substituted in Medical Devices. Sammenfatning og konklusionerPå basis af studier af de blødgørende stoffer og stofgrupper, der er kommercielt tilgængelige i dag, er der udvalgt og undersøgt ni stoffer. Der blevet fremstillet PVC-kompounder med hvert af disse stoffer som blødgøringsmiddel. Disse kompounder er blevet prøvet for en række udvalgte egenskaber, som anses for at være primære udvælgelseskriterier for anvendelse i medicinsk udstyr. Alle kompounderne var lette at fremstille, og det var uden særlige problemer at forarbejde alle kompounderne ved sprøjtestøbning. Det er blevet forsøgt at rangere de undersøgte blødgørende stoffer i sammenligning med en DEHP-blødgjort PVC-kompound. Nogle har lidt mindre styrke, nogle lidt mindre brudtøjning (relativ brudforlængelse), og nogle har en højere cold flexibility-temperatur. Ingen af stofferne er blevet forkastet som potentielle alternativer til DEHP. Imidlertid kræves der mange flere data, før man kan erstatte DEHP i medicinsk udstyr. 1 ObjectiveThe objective of this project is to select and evaluate Plasticisers for PVC for Medical Devices using DEHP as a benchmark. The selection has been carried out on the basis of commercially available Plasticisers that are presumed to be suitable for use as primary Plasticisers with PVC materials used for Medical Devices. The substances have been selected and evaluated as regards the requirements defined for Medical films and tubings. No new Plasticisers have been developed. However, considerations have also been given to other substances (e.g. polymeric substances) on the market, which might be suitable as Plasticisers for PVC for Medical applications. On the basis of the results of testing conducted in the project an attempt has been made to rank the investigated Plasticisers and PVC compounds according to their probability for success for use in Medical device applications. It is the intention of the project partners in a subsequent project for further investigations to be able to continue with the manufacture and testing of specific Medical Devices (e.g. catheters and drainage bags) made from the most promising compounds. 2 BackgroundIt is experienced that it is extremely complicated to find alternative materials to PVC in Medical device applications; reference to - among others - "Muligheder for substitution af PVC i udvalgte hospitalsartikler", Arbejdsrapport fra Miljøstyrelsen nr. 17/1991 ("Possibilities for substitution of PVC in selected hospital articles", Working report from the Danish Environmental Protection Agency No. 17/1991). Furthermore, according to the Danish EPA’s "Handlingsplan for at reducere anvendelsen af phthalater i blød plast" (Action Plan for reducing and phasing out phthalates in soft plastics, Ministry of Environment and Energy, June 1999), Medical Devices have been selected as a field of high priority requiring a particular effort to substitute phthalates as plasticising agents. According to the action plan, Medical Devices are a field of high priority, because of their migration from the plastic and subsequent exposure and possible adverse effects to patients. The world market for plastics for the production of Medical Devices accounts for DKK 35 – 40 billions (ref. 1). Hereof PVC for disposable articles accounts for approximately one third. Every year approximately 150.000 tons of PVC is produced world wide for the Medical market (ref. 2) corresponding to 1 – 2 % of the total market for PVC. In Denmark the turnover of Medical Devices in plastics accounts for approximately DKK 7 billions (ref. 3). Approximately 97 % hereof are being exported (ref. 3). The largest quantity is disposable articles mainly different sorts of catheters, suctions, drains and urine and colostomy bags. These many types of relatively low-cost disposable articles have formed a basis for and made it possible to introduce many of the new treatments that are being used today. Generally, in each case of hospitalisation the patient will come into contact with some of these disposable articles. Due to the rich possibilities of variation, which can be achieved in e.g. properties like flexibility, strength, barrier properties and transparency, plasticised PVC has been proven to be particularly suitable for these applications. These properties are to a high extent conditional on the addition of Plasticisers to the PVC resins. In these types of Medical Devices the addition of Plasticisers typically varies from approximately 5 % by weight up to approximately 45 %; mainly 30 – 45 %. Totally dominating as plasticiser is di(2-ethylhexyl) phthalate (DEHP), with which one has more than 47 years of experience in Medical Devices (ref. 4). Furthermore, in the European Pharmacopoeia DEHP is the only plasticiser which is listed for use in those kind of products (ref. 8a, 8b and 9). As the European Pharmacopoeia is put on the same footing as the Directive for Medical Devices (ref. 10), which was put into force in July 1998 the manufactures of Medical Devices are left with a serious dilemma. This is because no other plasticiser is listed in the European Pharmacopoeia and using another plasticiser would mean that the device manufacturer would have to declare that such a device does not conform to the compositional requirements of this Pharmacopoeia. Therefore, a development study and an investigation regarding Plasticisers are highly needed. Any positive result is highly expected to form a basis for a decision in "Group 16 of the Council of Europe" to point out other Plasticisers for consideration and inclusion in future amendments of the Pharmacopoeia. During recent years the environmental aspect by the use of phthalates has been studied in many relations (e.g. ref. 5, 11, 12 and 13). The Swedish government has proposed the European Commission to initiate a risk assessment of DEHP. However, other aspects will be important regarding the use of phthalates in Medical Devices. It is known that the Plasticisers migrate to the surface of the plasticised PVC article, where it could cause a relative risk regarding the biocompatibility (ref. 6, 7, 14 and 15). Moreover, during recent years the potential for reprotoxic effects of DEHP has been observed in animal studies and whilst there is no knowledge in humans the fact that it has been observed in animals remains a significant concern (ref. 42). Complicating the issue is that phthalates with different alkyl chain length behave differently in biological situations (like the case with different primary alcohols). 3 Procedure
3.1 Feasibility studyIn phase one of the project, a market survey has been carried out for the relevant Plasticisers based on the requirements, the wishes and the expectations outlined by the project participants. Relevant substances has been selected and evaluated in comparison with a selected DEHP plasticised PVC material as a reference compound. The resulting PVC compounds had also been briefly evaluated in comparison with a relevant non-PVC based plastic material. The development in PVC Plasticisers during the project period has simultaneously and continuously been observed. As an alternative non-PVC material an ethylene-vinyl acetate copolymer has been chosen. 3.2 Industrial researchIn phase two of the project, PVC compounds with a limited number of the selected Plasticisers have been prepared and tested for relevant properties. Each of these compounds has been prepared as granulates, from which appropriate test specimens have been made by injection moulding. From the compounds also film samples for testing have been made by roll milling. 3.3 Publication and informationThe feasibility study of this project has been presented and discussed at a seminar held at Aarhus University Hospital (Skejby Sygehus) in Århus, Denmark in June 2001. The title of the seminar was "PVC free in Århus County"; the title of the presentation was "Alternative Plasticisers (- an international project)". Additionally, the project has been presented at the 16th International Conference Medical Plastics 2002 held in Copenhagen late August 2002. Furthermore it will be presented in the Danish magazine Plast Panorama Scandinavia. 4 Activities during the projectDuring the work, twelve working group meetings and two reference group meetings have been held. Furthermore, a meeting has been held with a representative from Reilly Chemicals, a company producing Plasticisers for PVC. Three members of the working group have visited University of Strathclyde to present and discuss the project with Professor James Courtney, Bioengineering Unit. Finally, a number of meetings have been held with the Danish partners. Further, the group has used the expertise of Laporte Performance Chemicals UK Ltd in the selection of non-DEHP Plasticisers. Hydro Polymers Limited have prepared the PVC compounds. Laporte Performance Chemicals UK Ltd have supplied one plasticiser. Danish Technological Institute, Plastics Technology have injection moulded tensile test specimens and square samples for testing of other properties. Papyro-Tex A/S have prepared film samples by roll milling and determined tensile properties on the film samples. Danish Technological Institute, Plastics Technology have determined tensile properties, indentation hardness, density and cold flexibility temperature on injection mouldings. Danish Technological Institute, Packaging and Transport have determined light transmission on film samples. 5 The feasibility study
5.1 Plasticiser selection criteriaThe relevance of the applied selection criteria for Plasticisers for PVC for Medical Devices is described below. The list refers to the criteria mentioned in the plasticiser performance matrix, which is described in clause 6.2 and enclosed as appendix 1. 5.1.1 AvailabilityA plasticiser needs to be commercially available in large quantities (ton lots) to satisfy current demand for plasticised PVC for Medical applications. 5.1.2 Compatibility towards PVC resinsThe compatibility could be expressed as: To what extent is a substance capable of forming a stable compound with the polymer? The compatibility is often measured as the solution temperature, i.e. the temperature at which a mixture of plasticiser and suspension PVC apparently changes to a single-phase state. A plasticiser needs to be compatible with PVC resins. If a substance is incompatible it will exude to the surface of an article and can be more easily extracted; i.e. an incompatible plasticiser will not plasticise PVC properly. Furthermore, a plasticiser should be tolerant to the stabilisers and other additives in the compound to avoid exudation in the process or/and a sticky surface of the final article. The volatility of the plasticiser should be low - at least not higher than that of DEHP. 5.1.3 Plasticising efficiencyThe plasticising efficiency of a plasticiser determines the level of plasticiser in a compound that is needed to achieve the required degree of modification of the compound. In this work the hardness of PVC compound has been chosen as the reference parameter. The more efficient the less plasticiser will be required. The efficiency is an important property when determining overall cost. 5.1.4 ProcessabilityA PVC material is made up from a blend of ingredients: PVC resin (the polymer that makes the material a plastic), plasticiser(s), stabilisers and lubricants. The ingredients are blended together in a high-speed mixer or a ribbon blender. During this process the plasticiser is absorbed into the PVC resin particles. This blend can then be processed directly into an article by extrusion, by injection moulding and by calendering. It can also go through an intermediate step of compounding. This is where the blend is fed into an extruder and by means of heat and pressure it becomes molten. The molten mass is extruded (pressed through a spaghetti die) and the solidified strands are cut into small pellets called granulate. The pellets are cooled from approx. 150°C to ambient temperature. The pellets can then be used to form articles by extrusion, by injection moulding and by calendering. Injection moulding A plasticiser should be sufficiently stable to withstand the heat and the deformation associated with the injection moulding process. No sweating should occur. A low vapour pressure is also desirable. Extrusion A plasticiser should be sufficiently stable to withstand the heat and the deformation associated with the extrusion process. No sweating should occur. A low vapour pressure is also desirable. Calendering A plasticiser should be sufficiently stable to withstand the heat and the deformation associated with the calendering process. 5.1.4.3 Fabrication operations Welding and bonding A plasticiser should not harm the assembly process. No sweating should occur. Machinability and printability A plasticiser should not harm the machining or the printing processes. No sweating should occur. 5.1.4.4 Post fabrication operations Radiation sterilisation A plasticiser should be sufficiently stable towards the energy disposition associated with the radiation sterilisation process. No sweating should occur. Ethylene oxide (EO) sterilisation A plasticiser should be sufficiently stable towards the heat, humidity and chemicals associated with the ethylene oxide sterilisation process. No sweating should occur. Steam sterilisation A plasticiser should be sufficiently stable towards the heat and humidity associated with the steam sterilisation process. No sweating should occur. A low vapour pressure is also desirable, so the plasticiser does not distil away. 5.1.5 CostThis breaks down into two sections and related to the overall cost/performance/efficiency of the system. Plasticiser cost combined with plasticising efficiency needs to be as low as possible to keep materials cost low and to remain competitive. Processing cost needs to be considered. The plasticiser has major influence on processing cost (see Processability) Toxicity is the effect of the plasticiser on life forms and plant material. Plasticiser needs to have low toxicity - food contact approval being one means of determining current toxicity status. Plasticiser should be safe to handle and not cause any adverse effect upon industry employees. Material will be handled in large quantities i.e. > 1 tonne. In addition products manufactured from the compound will be widely handled by Medical staff and come into skin contact with the patients and it is imperative that there is no allergic reaction to such products as observed by some latex products etc. Medical Devices made from this material should have no adverse effect on the users and the material should meet USP class VI (USP = United States Pharmacopoeia). Material should also not interact with substances (e.g. drugs) that it will come into contact with. Drug efficiency should not be impaired. These aspects has primarily been described for DEHP. 5.1.7 Environmental statusEmissions during plasticiser manufacture The production process should not have any detrimental effect upon the environment. Waste products and emissions need to be considered. Emissions during processing Material should not have any adverse effects on the environment during processing. Emissions and residues should be taken into account. Emissions in use Material should not have any adverse effect on the environment during use Due to the risk of spreading of infections all Medical Devices should be disposed of via incineration. Therefore plasticiser should be suitable for incineration without adverse effects i.e. emissions or residues. 5.1.7.3 Sustainable development Plasticiser selection should consider whether the material can demonstrate sustainability, i.e. materials made from natural products being more sustainable than materials made from non renewable resources. 5.1.8 Physical properties of plasticiserColour Colour is considered important in that it conveys "purity of product" to the user. Plasticisers should give colourless compounds and articles. A lot of PVC additives either produce materials that are semi-opaque or yellow in appearance. They are by the Medical industry and the hospital staffs perceived to be imperfect or contaminated. Clarity Plasticiser needs to give a clear/transparent material. This allows for the end user to see the contents of any article or device made from the material. Material made with plasticiser should not have any odour, as odour indicates emission. 5.1.9 Physical properties of compoundsTensile strength The material needs to have sufficient strength to ensure that the article remains durable and intact throughout its entire service life. Any likely abuse of material needs to be considered. Properties need to be maintained throughout the service life of the product. Cold flexibility The material needs to retain its flexibility at low temperatures, as products are likely to be used or stored in low temperature environments. This property needs to be maintained throughout the service life of the product such as blood storage. Elastic recovery The rate or degree at which a material returns to its original shape after being deflected - the elastic recovery - is important at many applications and especially in flexible PVC tubing for use in peristaltic pumping applications. 5.1.10 Public perceptionThe public perception is the way the general public reacts to a description of a material or a product. (E.g. a substance called di-hydrogen oxide would probably be considered bad, but described as water it would be considered harmless). 5.2 Plasticiser performance matrixA performance matrix for Plasticisers for PVC for Medical applications has been prepared based on the best knowledge collected by the project partners (see appendix 1). Data and comments in the matrix are primarily based on the experience of the partners and on the general literature (e.g. ref. 19 and 34). In the performance matrix the term "Unknown" means unknown to the project workers for the moment. Many aspects have not been investigated and therefore data are not existing. Some aspects have been considered as being less important and therefore no effort has been made to search for data. An asterisk (*) refers to knowledge transferred from DEHP or DEHP plasticised PVC. Phthalates being assessed in the risk assessment program in the EU are marked with EU). The plasticising efficiencies indicated are based on information from Hydro Polymers. The abbreviations used in the matrix are explained in table 1: Table 1
5.3 Substances selected for further investigationThe substances listed below are considered as having the highest potential for success as a plasticiser for PVC for Medical applications and therefore they have been selected for further investigations. PVC compounds based on these substances have been prepared and substantial properties have been determined by testing and compared with the properties of a reference PVC compound plasticised with DEHP, so DEHP is also in the list: Table 2
The arguments for selecting or rejecting each of the substances are as follows DEHP: Yes! DEHP is necessarily selected as a reference plasticiser. DEHP is available in one grade that is pure enough to be Medical. DINP: Yes! During the work it became obvious to include diisononyl phthalate and diisodecyl phthalate, as they in the EU studies appear to be coming out reasonably favourable regarding their risk assessments. Anyway, it is too narrow to consider phthalates as a uniform group of substances; phthalates should be considered as individual substances. DINP is used in food contact and in toys, and we consider it as a potential substitute for DEHP for Medical Devices. Among phthalates DINP is probably the best alternative to DEHP. Commercial DINP is always a mixture of isomers, the composition of which varies from producer to producer. Depending on the way of synthesis DINP exist as two different products with two CAS numbers. Therefore the product to be investigated has been specified in detail by selecting a specific product. DIDP: No! One alternative phthalate is sufficient. Other phthalates: No! One alternative phthalate is sufficient. DEHA: Yes! DEHA is already being used for Medical applications. Some ecotoxicity problems have been considered. DEHA is available in one grade that is pure enough to be Medical. It is being used by at least one company. Other monomeric adipates: No! One monomeric adipate is sufficient. Polymeric adipates: Yes! A polymeric adipate is considered as the sole potentially relevant polymer to substitute DEHP as a primary plasticiser in PVC. Polymeric adipates are mixtures of polymers of different chain length, the composition of which varies from producer to producer. Therefore a specific grade to be investigated has been chosen and the product has been specified in detail. TEHTM: Yes! TEHTM is available in Medical grades and is already used in e.g. bags and infusion sets. ATBC: Yes! ATBC is currently being used in some special Medical applications. ATHC: No! No information of the existence of ATHC in Medical grades or Medical applications of ATHC has been found; one citrate is sufficient. BTHC: No! Occupational and health problems have been reported from the State University Hospital in Denmark, where BTHC plasticised PVC blood bags are being handled at the blood bank.One citrate is sufficient. Benzoates: Yes! Only little information is available but they seem promising. A choice between a number of products available from at least two suppliers has been made. Sulphonates: No! Sulphonates are rejected mainly because of the emission of SO2 (sulphur dioxide) during incineration as waste. Phosphates: No! Phosphates have poor technical properties, and they are forbidden according to the Nordic Pharmacopoeia (Ph. Nord. 63). Soya Bean Oil (epoxidised): No! Soya bean oils have limited compatibility and the processability is poor. However, soya bean oils are readily used as secondary Plasticisers and as stabilisers. DEHS: Yes! Di(2-ethylhexyl) sebacate has extensive FDA approval and is frequently used in the cosmetic industry. It is commercially available from many sources. Note: It is manufactured from sebacic acid, which is a by-product from cracking of castor oil. Thus is it produced from natural products. DEHZ: No! Di(2-ethylhexyl) azelate is commercially available from only a very few manufactures. The main raw material, azelaic acid, is only available from one source. The performance characteristics of DEHZ and DEHS are similar. Most compounders prefer to use DEHS. Naphthenates: No! Naphthenates are not commercial available in ton lots. Polyhydric alcohol esters: No! They are not commercially available in ton lots, not tested and probably the existing grades are not suitable for Medical applications. Aliphatic glycol esters. No! They are not commercially available in ton lots, not tested and probably the existing grades are not suitable for Medical applications. Ethylene-acrylate-carbon monoxide terpolymer (Elvaloy®): Yes! According to the producer these products can be used as a plasticiser on there own. Though only one producer is known it was considered worthwhile to include a suitable product for further investigation. Nitrile rubber: No! Generation of hazardous fumes when incinerated. Polyurethane: No! Polyurethanes are used as solid Plasticisers in conjunction with a primary plasticiser. They are not suitable as primary Plasticisers. Generation of hazardous fumes when incinerated. EVAC: No! EVAC is used as a solid plasticiser in conjunction with a primary plasticiser. It is not suitable as a primary plasticiser. Metallocene catalysed polyolefines: No! They are not readily available. The latest published development has not shown any reliable potential. They have limited compatibility with PVC, as polyolefines and PVC are generic very different from each other. DACM: No! DACM is commercially available only in small quantities. No Medical application is known. High price! Esters of palm oil, castor oil, corn oil and rapeseed oil: No! Limited availability - unsuitable as primary Plasticisers - no potential as substitutes for DEHP. An exception is castor oil, in that sebacates are based on castor oil. 6 Experimental6.1 Preparation of compounds, films and test specimens6.1.1 Preparation of PVC compounds plasticised with the selected substancesApprox. 25 kg of test compounds based on each of the selected substances as a plasticiser were prepared and pelletised at Hydro Polymers with the compositions shown in Table 3 below. As a reference compound a standard DEHP plasticised PVC compound with a Shore A hardness of 80 was chosen, and the Shore A hardness of the test compounds should be as near as possible to 80 for comparison reasons. Table 3
1) Sources of the ingredients are listed in appendix 3 6.1.2 Preparation by injection moulding of specimens for material characterisationFrom the prepared PVC compounds dumbbell shaped tensile test specimens of type 1A according to ISO 527-2:1993 and square test specimens 4 mm thick and 50 mm in side length were made by injection moulding at the Danish Technological Institute. The detailed injection moulding reports are enclosed as appendix 2. Table 4 shows the injection moulding parameters used. Table 4
6.1.3 Preparation by roll milling of film samples for testingFrom the prepared compounds 185 - 400 µm thick film samples were made by direct roll milling at PapyroTex. The temperature of the front roll was 166ºC; the temperature of the back roll was 160ºC. Prior to testing the film samples were conditioned at room temperature for four days. 6.2 Characterisation of the prepared compounds and of the alternative non-PVC materialThe test program was conducted at Danish Technological Institute, Centre for Plastics Technology except from the tensile test of film samples, which was performed at the laboratory at Papyro-Tex. The laboratory at Danish Technological Institute, Centre for Plastics Technology is accredited according to DS/EN ISO/IEC 17025 to perform a long range of tests on plastics and similar materials. 6.2.1 Tensile properties determined on injection moulded specimensTest method: ISO 527-2, specimen type 1A. Crosshead speed 100 mm/min. The detailed test reports are enclosed in appendix 4. Table 5
*) No break at this strain
Fig. 1
Fig. 2 6.2.2 Density of the prepared compounds The density of the prepared PVC compounds and of the alternative plastic material was determined on square injection moulded specimens. Test method: ISO 2781 method A, ver. 1. Table 6
Fig. 3 6.2.3 Indentation hardness determined on square injection moulded specimensTest method: DS/EN ISO 868:1998 read after 15 seconds. Table 7
*) This value is beyond the interval valid for Shore A
Fig. 4 6.2.4 Cold flexibilityThe cold flexibility temperature was derived from the torsional moduli at varying temperatures determined on plane-parallel specimens cut out from injection moulded tensile test specimens. Test method: ISO 458/1-1985. The cold flexibility temperature is defined as the temperature, at which the torsional stiffness, determined by apparent torsional modulus testing, is 310 N/mm at an angular deflection value of 200 degrees. The resulted graphs are enclosed in appendix 5. Table 8
*) These expected values are derived from ref. 19 and
interpolated to the actual hardness values
Fig. 5 6.2.5 Tensile properties determined on roll milled film specimensTest methods: ISO 527-3, specimen type 2. Width 10 mm, length 150 mm and clamp distance 100 mm. Crosshead speed 200 mm/min. Prior to testing the film samples were conditioned at room temperature for four days. The mean values were derived from five single values. These tests were performed at Papyro-Tex. The detailed test reports are enclosed in appendix 6. Table 9
Fig. 6
Fig. 7 6.2.6 Light transmission determined on roll milled film specimensTest method: USP XXIV <661> with the exception for the washing and drying of the film samples and with a wider range for the light transmission measurements (290 nm to 800 nm). Instrument model: Perkin Elmer LAMBDA 18; data interval: 1.0000 nm; scan speed: 240.00 nm/min; slit width: 2.0000 nm; smooth bandwidth: 0.00 nm. The single light transmission graphs are enclosed in appendix 7. Table 10
1) Shiny side towards the light source
Fig. 8 6.3 Total assessmentTable 12 shows an attempt to make a total assessment Table 12 7 Discussion7.1 Uniformity of the compoundsAll the compounds are apparently uniform, as there is no sign of phase separation. 7.2 Visual assessment of the prepared mouldings and filmsThe injection mouldings prepared from the compounds plasticised with DEHP, DINP, DEHA, DEHS, TEHTM and ATBC look all alike, i.e. transparent, very slightly yellow and with a smooth and shiny surface. The benzoate and polyadipate plasticised mouldings are slightly more yellow. However, with all the compounds the yellowness is only visible by the naked eye through the approx. 4 mm thick mouldings, not through any of the film samples. The injection mouldings from the compound plasticised with EAC terpolymer have an uneven dull surface with indications of material flow directions. Because of the dull surface character it is difficult to compare the yellowness to that of the other compounds. Immediately the yellowness looks more like that of the benzoate and the polyadipate plasticised compounds. However, this yellowness is not visible in the film thickness. The EVAC mouldings are colourless. The surface is almost as shiny as that of the first mentioned six compounds. However, indications of material flow directions are slightly visible near the injection inlet point. Apart from the fact that all of the prepared film samples look fairly homogeneous, it makes no sense to visually assess the roll milled film samples, as they have been prepared by a method that is not representative for the industrial manufacture of PVC films in large quantities. 7.3 Evaluation of the test results7.3.1 HardnessFor comparison reasons the PVC test compounds were prepared with the attempt to obtain the same hardness as near as possible to Shore A 80. The hardness of the reference DEHP plasticised compound has been determined to be 82. That of the alternative compounds differs between 78 and 84, except the EAC terpolymer plasticised compound, which has a Shore A hardness of 94 (a value that is beyond the interval valid for Shore A). The hardness of the chosen alternative plastic material, EVAC, is 79. The hardness values found for the test compounds plasticised with DEHP, DEHA, DEHS, TEHTM and polyadipate are within two units from the values that could be expected according to the literature (ref. 19). Transformation from Shore A values to British Standard Softness Numbers can be found in the literature e.g. ref. 19 and 20. It seems likely that any wanted specified interesting hardness of PVC compounds plasticised with the selected alternative Plasticisers - with the exception of the EAC terpolymer - is possible. Obviously it is possible to purchase an EVAC with a Shore A hardness of approximately the reference value of 80. 7.3.2 DensityThe density of the tested compounds varies from that of the DEHP plasticised compound with from -39 kg/m³ to +60 kg/m³ (from -3 % to +5 %) for the PVC compounds. The density of the EVAC is 951 kg/m³, which is to be expected as this material is based on olefins. 7.3.3 Mechanical propertiesThe tensile strength of injection moulded samples of the PVC compounds vary from 12.6 MPa to 19.7 MPa. The strength of the DEHP plasticised compound is 14.7 MPa. The highest value (19.7 MPa) was found at the compound plasticised with the EAC terpolymer. Among the monomer plasticised compounds the highest value is 16.8 MPa. With a tensile strength value of 6.3 MPa the strength of EVAC is less than half that of the reference PVC compound. For some Medical applications, the EVAC probably results in uninterestingly weak compounds. Due to different crosshead speeds during testing it is expected that the tensile strength values determined on the film samples are significantly higher than the values determined on the injection moulded specimens. The test results show 14 – 40 % higher tensile strength values determined on the film samples (at crosshead speed 200 mm/min) than on the injection moulded specimens (at crosshead speed 100 mm/min). The results determined on film specimens for DEHP, DEHA and TEHTM do not contradict with the expected values found in the literature (ref. 19). The tensile strength of the EAC terpolymer plasticised PVC compound is 34 - 38 % higher than that of the reference compound; however, the samples of this compound is significantly thicker. Determined on the 4 mm thick specimens at 100 mm/min crosshead speed the highest tensile strength value among the PVC compounds is approx. 34 % higher than that of the reference compound; the lowest one is approx. 14 % lower than that of the reference compound. Determined on the film samples at 200 mm/min crosshead speed the highest value is approx. 38 % higher and the lowest value approx. 28 % lower than that of the reference compound. 7.3.3.2 Tensile strain at break The tensile strain at break of injection moulded samples of the PVC compounds vary from 102 % to 279 %. The strain at break of the DEHP plasticised compound is 234 %. The highest value (279 %) was found at the compound plasticised with the DEHA and the lowest value (102 %) at the EAC terpolymer plasticised compound. With a tensile strain at break of more than 934 % the strain of EVAC is more than four times that of the reference PVC compound. Due to different crosshead speeds during testing it is expected that the tensile strain values determined on the roll milled films (at crosshead speed 200 mm/min) are significantly higher than the values determined on the injection moulded specimens (at crosshead speed 100 mm/min). This is confirmed by the test results. The tensile strain at break values determined on film specimens for DEHP, DEHA and TEHTM do not contradict significantly with the expected values found in the literature (ref. 19), actually they are some 19 % higher. The tensile strain at break of the EAC terpolymer plasticised PVC compound determined at 200 mm/min crosshead speed is 20 % lower than that of the reference compound; determined at 100 mm/min it is 56 % lower. The actual values found are 333 % and 102 % respectively; the former is more than three times the latter. For the other compounds the high-speed results are 37 - 93 % higher than the low-speed values. Apparently the EAC terpolymer plasticised compound is significantly more sensitive to strain speed than the other ones. 7.3.3.3 Cold flexibility temperature The determined cold flexibility temperature values are very close to the expected values. However, for the EVAC and the PVC compounds plasticised with benzoate and EAC terpolymer no information on expected values was available. The cold flexibility temperature are approx. -20° C for PVC compounds plasticised with DEHP, DINP, TEHTM and ATBC. For DEHA and DEHS plasticised compounds the value are significantly below -40° C. For the benzoate plasticised compound it is approx. -3° C, and for the compound plasticised with polyadipate it is -10° C. In comparison with DEHP, the benzoate and the polyadipate seem critical as substitutes for DEHP. The cold flexibility temperature of the compound plasticised with EAC terpolymer is as high as 11° C! This high value probably disqualifies the EAC terpolymer as a substitute for DEHP for PVC for Medical Devices. The value for EVAC is approx. -36° C. 7.3.4 Light transmissionLight transmission values of 90 to 92 % in the visible wavelength range 450 nm to 800 nm does not disqualify any of the tested PVC compounds nor the EVAC. 7.4 CostThe current cost relations of the used plasticiser products are shown in table 11. Table 11
7.5 Comments to each of the tested plasticising substancesDINP DINP is not available in Medical grades. Concern on the available purity has been expressed. The current price is as expected. Two CAS numbers exist. DEHA The current price of the used DEHA is more than twice the expected. According to a Danish EPA project, DEHA is considered more aqua-toxic than DEHP (ref. 31 and 32). DEHS The current price of the used DEHS is in the low end of the expected price interval. TEHTM: Trimellitates are reported to migrate to the blood faster than DEHP (ref. 33), which, however, contradicts with the experience of the project partners. The price of the used TEHTM is significantly lower than expected. Benzoate: According to correspondence with Velsicol Chemicals, which produces benzoates, they are reluctant to consider Benzoflex 9-88 as a suitable plasticiser for PVC for Medical products. One obvious drawback is the poor resistance to extraction by water, which is an important consideration for PVC Medical products. The price of the used benzoate is slightly lower than expected Polyadipate Polyadipates have successfully been used as Plasticisers for Medical grade PVC since around 1980. The price of the used polyadipate product is as expected. ATBC The price of the used ATBC is twice the expected. EAC Terpolymer The price of the used Elvaloy product is as expected. 7.6 Films versus tubingsIn this project all the specimens were prepared only by injection moulding and the film samples only by roll milling, so this gives no basis for judging the ability of the prepared compounds to be processed by extrusion and calendering. So far no arguments were found to distinguish between compounds for tubings and compounds for films. 7.7 Preliminary ranking of the investigated substances and compoundsBased on the performed tests in this project DINP, DEHA and ATBC appear to give compounds with similar properties as DEHP. A proper raking of the other plasticising substances is not possible to make as the drawbacks found concern different properties. The application in question of the final product will determine the required materials properties. The investigated polyadipate shows a drawback in that the cold flexibility temperature of the compound is some 10ºC higher than that of the DEHP plasticised compound. TEHTM shows a decrease in the tensile strain at break and can only be used if this is acceptable for the application in question. DEHS gives compounds with a decreased tensile strength, and the tensile strain at break is also lower at least in film thickness. Depending on the specific application DEHS might be an interesting substitute for DEHP. It would be relevant to verify this apparent similarity in a succeeding investigation as a new round of compounding and characterisation, before one can select appropriate alternatives for the next tasks, e.g. the biological assessment etc. 7.8 General remarksIn the project period a new plasticiser has been reported. BASF has introduced di-isononyl-cyclohexane-1,2 dicarboxylate under the trade name Hexamoll® DINCH. They claim it to be suitable in PVC applications that are particularly sensitive from the toxicological point of view. Information on the product can be found on their homepage on Internet (ref. 35). The possibilities for replacing plasticised PVC with other plastic materials are multiple and many attempts have been made during recent years. However, each single application has to be investigated on its own. This might very well include a total materials selection process. An example on a newly reported replacement material for certain Medical applications is Dow Chemical’s work with a metallocene catalysed polyolefin film called Corvelle (ref. 36). 8 ConclusionThe investigations conducted in this project confirm that an extensive effort is needed before one can decide to substitute di(2-ethylhexyl) phthalate (DEHP) with any other plasticiser. It is a well-known fact that DEHP is by far the most investigated PVC plasticiser substance. In the plasticiser performance matrix created in this project DEHP is the only substance, of which no information is lacking. No matter which alternative to DEHP one might want to use, a substantial new knowledge must be generated. Based on this project, i.e. within the limitations of the investigated properties, it seems likely, that diisononyl phthalate (DINP), di(2-ethylhexyl) adipate (DEHA) and acetyltributyl citrate (ATBC) can give PVC compounds with properties that are comparable to those of DEHP plasticised PVC. The only drawback (apart from the cost) with the investigated polyadipate seems to be the poorer cold flexibility of the compound. The cold flexibility temperature is some 10°C higher than that of the DEHP plasticised compound. The values found are -10°C for the polyadipate and -20°C for DEHP. Even though the compatibility towards PVC has been reported to be limited, no drawback was found in this investigation that can be explained by this. Triethylhexyl trimellitate (TEHTM) also looks interesting, if a decrease in the tensile strain at break can be accepted for the application in question. Di(2-ethylhexyl) sebacate (DEHS) gives compounds with a substantially lower tensile strength, and the tensile strain at break is also lower at least in film thickness, but depending on the specific application it might also be an interesting replacement for DEHP. The investigated benzoate (dipropylene glycol dibenzoate) results in a compound with a cold flexibility that is worse than with the polyadipate; the cold flexibility temperature value found is -3°C. Furthermore, the tensile strain at break is substantially decreased - nearly 30 % tested at a crosshead speed of 200 mm/min. The most important disadvantage (apart from the cost) of the investigated ethylene-acrylate-carbon monoxide terpolymer (EAC terpolymer) is the very poor cold flexibility of the compound. The cold flexibility temperature was found to be as high as +11°C. The tensile strength of PVC compounds plasticised with this substance is some 35 % higher than that of compounds plasticised with DEHP. The tensile strain at break, however, is reduced to 44 % determined at a crosshead speed of 100 mm/min and to 80 % determined at 200 mm/min. Presumably, the potential for use for Medical applications is limited due to these limited properties. To replace plasticised PVC with another plastics material is highly depending on the actual final product and its application. In this project an ethylene-vinyl acetate copolymer has been considered. It is worth to note that EVAC is known to emit acetic acid during processing like extrusion or injection moulding. The final evaluation can only be made after assessment of biological properties and further investigation of Medical articles like tubings, catheters and bags made of the relevant compounds. However, this is not included in this project but is expected to be made in a subsequent project. 9 Proposal for further workAccording to the original proposal for this project (ref. 41), which is shown in the project flow diagram on the next page, the manufacturing of Medical tubes and bags and further physical and chemical characterisation of those articles should succeed this project. The need for more data and experience has not decreased during recent years. The Swedish National Board of Health and Welfare have expressed their concern for the risk of the patients safety associated with (uncritical - authors remark) replacement of phthalates in PVC Medical Devices (ref. 37). The Public Health Notification by FDA's Department of health & human services by July 12, 2002 recommends as follows (ref. 38), which is based on the FDA CDRH assessment of DEHP from September 2001 (ref. 39 and 40): "Most important, you should not avoid the procedures cited above (a number of procedures that have been identified as posing the highest risk of exposure to DEHP in the patient treatment - authors remark) simply because of the possibility of health risks associated with DEHP exposure. The risk of not doing a needed procedure is far greater than the risk associated with exposure to DEHP. For some of the above procedures, PVC Devices that do not contain DEHP can be substituted, or Devices made of other materials (such as ethylene vinyl acetate (EVAC), silicone, polyethylene or polyurethane) can be used, if available. If PVC Devices containing DEHP must be used, you may be able to minimise exposure to DEHP by, for example, using the freshest possible blood products stored at the lowest possible temperature, or by using heparin-coated ECMO circuits. We recommend considering such alternatives when these high-risk procedures are to be performed on male neonates, pregnant women who are carrying male fetuses and peripubertal males… For other patient groups, who are presumably at lower risk, the decision to use DEHP alternatives must take into account the Medical advantages and drawbacks of the substitute materials and their availability." A wide agreement appears on the necessary cautiousness to be shown in this question. It is still the recommendation and the intention of the project group to proceed with the investigation of DEHP alternatives according to the original proposal mentioned above.
10 References
Appendix 1
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Substance |
|
||
Abbreviation |
Chemical nature |
CAS No. |
Supplier or producer |
PVC |
Polyvinylchloride |
|
Norsk Hydro |
DEHP |
Di(2-ethylhexyl) phthalate |
117-81-7 |
BP Chemicals Ltd. |
ESBO |
Epoxydised soya bean oil |
|
Crompton Vinyl Additives GmbH |
Stabiliser |
A calcium-zink compound |
|
Crompton Vinyl Additives GmbH |
DINP |
Diisononyl phthalate |
68515-48-0 |
ExxonMobil Chemical |
DEHA |
Di(2-ethylhexyl) adipate |
103-23-1 |
BASF plc |
DEHS |
Di(2-ethylhexyl) sebacate |
122-62-3 |
Laporte Performance Chemicals |
TEHTM |
Tri(2-ethylhexyl) trimellitate |
3319-31-1 |
Lonza Intermediates and Adeditives |
Benzoate |
Dipropylene glycol dibenzoate (> 5 % monoester) |
27138-31-4 (125457-59-2) |
Velsicol Chemical Corporation |
Polyadipate |
A polyester based on adipic acid/neopentyl glycol/1,4 butane diol modified with a mono alcohol in the range C6 - C12 |
- |
Kemira Polymers |
ATBC |
Acetyltributyl citrate |
77-90-7 |
Pfizer Chemicals |
EVA Terpolymer |
Ethylene terpolymer with n-butyl acrylate, fillers, additives, n-butylacrylate |
141-32-2 |
Du Pont (U.K.) Limited |
EVAC |
Ethylene-vinyl acetate plastic |
|
Du Pont Industrial Polymers |
Trækprøvning
Logbog for trækprøveapparat / kunde |
||||||
Ordrenr. |
DP 01036 Clear 97 DOP |
|||||
Kvalitet / Farve |
|
|||||
Tykkelse |
250 µm |
|||||
Narv |
|
|||||
Analyseresultater |
1 |
2 |
3 |
4 |
5 |
GNM. |
Trækstyrke MPa |
20,48 |
19,65 |
20,43 |
19,97 |
19,88 |
20,08 |
- Tværretning |
|
|
|
|
|
|
Brudforlængelse % |
426 |
414 |
408 |
412 |
415 |
415 |
- Tværretning |
|
|
|
|
|
|
Videre-rivestyrke N/mm |
|
|
|
|
|
|
- Tværretning |
|
|
|
|
|
|
10 - 50 % forlængelse |
|
|
|
|
|
|
- Tværretning |
|
|
|
|
|
|
I tilfælde af, at der ikke køres efter de fastsatte normer, skal dette anføres under
bemærkninger. analysebetingelserne beskrives.
| Trækstyrke | ISO 527-1 og ISO 527-3 |
| Brudforlængelse | ISO 527-1 og ISO 527-3 |
| Videre-rivestyrke | DIN 53363 10 / 50 % |
| Forlængelse | BS 3924 : 1978 |
Bemærkninger:_________________________________________________
_____________________________________________________________
Dato___14/5-01
Udført af____jo______
Reference:
DS/EN ISO 9001:2000 i 2216
Trækprøvning
Logbog for trækprøveapparat / kunde |
||||||
Ordrenr. |
DP 01037 Clear 97 DINP |
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Kvalitet / Farve |
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|||||
Tykkelse |
210 µm |
|||||
Narv |
|
|||||
Analyseresultater |
1 |
2 |
3 |
4 |
5 |
GNM. |
Trækstyrke MPa |
20,22 |
20,66 |
20,37 |
20,69 |
20,87 |
20,56 |
- Tværretning |
|
|
|
|
|
|
Brudforlængelse % - Længderetning |
387 |
381 |
384 |
385 |
369 |
381 |
- Tværretning |
|
|
|
|
|
|
Videre-rivestyrke N/mm - Længderetning |
|
|
|
|
|
|
- Tværretning |
|
|
|
|
|
|
10 - 50 % forlængelse - Længderetning |
|
|
|
|
|
|
- Tværretning |
|
|
|
|
|
|
I tilfælde af, at der ikke køres efter de fastsatte normer, skal dette anføres under
bemærkninger. analysebetingelserne beskrives.
| Trækstyrke | ISO 527-1 og ISO 527-3 |
| Brudforlængelse | ISO 527-1 og ISO 527-3 |
| Videre-rivestyrke | DIN 53363 10 / 50 % |
| Forlængelse | BS 3924 : 1978 |
Bemærkninger:_________________________________________________
_____________________________________________________________
Dato___14/5-01
Udført af____jo______
Reference:
DS/EN ISO 9001:2000 i 2216
Trækprøvning
Logbog for trækprøveapparat / kunde |
||||||
Ordrenr. |
DP 01038 Clear 97 DOA |
|||||
Kvalitet / Farve |
|
|||||
Tykkelse |
220 µm |
|||||
Narv |
|
|||||
Analyseresultater |
1 |
2 |
3 |
4 |
5 |
GNM. |
Trækstyrke MPa |
17,75 |
18,23 |
18,40 |
17,22 |
18,26 |
17,97 |
- Tværretning |
|
|
|
|
|
|
Brudforlængelse % |
401 |
406 |
415 |
402 |
431 |
411 |
- Tværretning |
|
|
|
|
|
|
Videre-rivestyrke N/mm - Længderetning |
|
|
|
|
|
|
- Tværretning |
|
|
|
|
|
|
10 - 50 % forlængelse - Længderetning |
|
|
|
|
|
|
- Tværretning |
|
|
|
|
|
|
I tilfælde af, at der ikke køres efter de fastsatte normer, skal dette anføres under
bemærkninger. analysebetingelserne beskrives.
| Trækstyrke | ISO 527-1 og ISO 527-3 |
| Brudforlængelse | ISO 527-1 og ISO 527-3 |
| Videre-rivestyrke | DIN 53363 10 / 50 % |
| Forlængelse | BS 3924 : 1978 |
Bemærkninger:_________________________________________________
_____________________________________________________________
Dato___14/5-01
Udført af____jo______
Reference:
DS/EN ISO 9001:2000 i 2216
Trækprøvning
Logbog for trækprøveapparat / kunde |
||||||
Ordrenr. |
DP 01039 Clear 97 DOS |
|||||
Kvalitet / Farve |
|
|||||
Tykkelse |
220 µm |
|||||
Narv |
|
|||||
Analyseresultater |
1 |
2 |
3 |
4 |
5 |
GNM. |
Trækstyrke MPa |
14,97 |
14,23 |
14,33 |
14,38 |
14,17 |
14,41 |
- Tværretning |
|
|
|
|
|
|
Brudforlængelse % |
362 |
348 |
345 |
341 |
355 |
350 |
- Tværretning |
|
|
|
|
|
|
Videre-rivestyrke N/mm - Længderetning |
|
|
|
|
|
|
- Tværretning |
|
|
|
|
|
|
10 - 50 % forlængelse - Længderetning |
|
|
|
|
|
|
- Tværretning |
|
|
|
|
|
|
I tilfælde af, at der ikke køres efter de fastsatte normer, skal dette anføres under
bemærkninger. analysebetingelserne beskrives.
| Trækstyrke | ISO 527-1 og ISO 527-3 |
| Brudforlængelse | ISO 527-1 og ISO 527-3 |
| Videre-rivestyrke | DIN 53363 10 / 50 % |
| Forlængelse | BS 3924 : 1978 |
Bemærkninger:_________________________________________________
_____________________________________________________________
Dato___14/5-01
Udført af____jo______
Reference:
DS/EN ISO 9001:2000 i 2216
Trækprøvning
Logbog for trækprøveapparat / kunde |
||||||
Ordrenr. |
DP 01040 Clear 97 TOTM |
|||||
Kvalitet / Farve |
|
|||||
Tykkelse |
220 µm |
|||||
Narv |
|
|||||
Analyseresultater |
1 |
2 |
3 |
4 |
5 |
GNM. |
Trækstyrke MPa |
18,54 |
18,41 |
18,00 |
18,49 |
17,48 |
18,18 |
- Tværretning |
|
|
|
|
|
|
Brudforlængelse % |
382 |
381 |
372 |
385 |
375 |
379 |
- Tværretning |
|
|
|
|
|
|
Videre-rivestyrke N/mm - Længderetning |
|
|
|
|
|
|
- Tværretning |
|
|
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|
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10 - 50 % forlængelse - Længderetning |
|
|
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|
|
|
- Tværretning |
|
|
|
|
|
|
I tilfælde af, at der ikke køres efter de fastsatte normer, skal dette anføres under
bemærkninger. analysebetingelserne beskrives.
| Trækstyrke | ISO 527-1 og ISO 527-3 |
| Brudforlængelse | ISO 527-1 og ISO 527-3 |
| Videre-rivestyrke | DIN 53363 10 / 50 % |
| Forlængelse | BS 3924 : 1978 |
Bemærkninger:_________________________________________________
_____________________________________________________________
Dato___14/5-01
Udført af____jo______
Reference:
DS/EN ISO 9001:2000 i 2216
Trækprøvning
Logbog for trækprøveapparat / kunde |
||||||
Ordrenr. |
DP 01041 Clear 97 Benzoflex 9-88 |
|||||
Kvalitet / Farve |
|
|||||
Tykkelse |
185 µm |
|||||
Narv |
|
|||||
Analyseresultater |
1 |
2 |
3 |
4 |
5 |
GNM. |
Trækstyrke MPa |
21,75 |
21,81 |
22,88 |
22,53 |
20,55 |
21,90 |
- Tværretning |
|
|
|
|
|
|
Brudforlængelse % |
292 |
299 |
324 |
296 |
272 |
296 |
- Tværretning |
|
|
|
|
|
|
Videre-rivestyrke N/mm - Længderetning |
|
|
|
|
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- Tværretning |
|
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10 - 50 % forlængelse - Længderetning |
|
|
|
|
|
|
- Tværretning |
|
|
|
|
|
|
I tilfælde af, at der ikke køres efter de fastsatte normer, skal dette anføres under
bemærkninger. analysebetingelserne beskrives.
| Trækstyrke | ISO 527-1 og ISO 527-3 |
| Brudforlængelse | ISO 527-1 og ISO 527-3 |
| Videre-rivestyrke | DIN 53363 10 / 50 % |
| Forlængelse | BS 3924 : 1978 |
Bemærkninger:_________________________________________________
_____________________________________________________________
Dato___14/5-01
Udført af____jo______
Reference:
DS/EN ISO 9001:2000 i 2216
Trækprøvning
Logbog for trækprøveapparat / kunde |
||||||
Ordrenr. |
DP 01042 Clear 97 Diolpate |
|||||
Kvalitet / Farve |
|
|||||
Tykkelse |
220 mm |
|||||
Narv |
|
|||||
Analyseresultater |
1 |
2 |
3 |
4 |
5 |
GNM. |
Trækstyrke MPa |
20,10 |
20,36 |
21,26 |
20,17 |
19,03 |
20,18 |
- Tværretning |
|
|
|
|
|
|
Brudforlængelse % |
370 |
368 |
407 |
369 |
360 |
374 |
- Tværretning |
|
|
|
|
|
|
Videre-rivestyrke N/mm - Længderetning |
|
|
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|
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- Tværretning |
|
|
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|
|
10 - 50 % forlængelse - Længderetning |
|
|
|
|
|
|
- Tværretning |
|
|
|
|
|
|
I tilfælde af, at der ikke køres efter de fastsatte normer, skal dette anføres under
bemærkninger. analysebetingelserne beskrives.
| Trækstyrke | ISO 527-1 og ISO 527-3 |
| Brudforlængelse | ISO 527-1 og ISO 527-3 |
| Videre-rivestyrke | DIN 53363 10 / 50 % |
| Forlængelse | BS 3924 : 1978 |
Bemærkninger:_________________________________________________
_____________________________________________________________
Dato___14/5-01
Udført af____jo______
Reference:
DS/EN ISO 9001:2000 i 2216
Trækprøvning
Logbog for trækprøveapparat / kunde |
||||||
Ordrenr. |
DP 01043 Clear 97 Citroflex |
|||||
Kvalitet / Farve |
|
|||||
Tykkelse |
220 µm |
|||||
Narv |
|
|||||
Analyseresultater |
1 |
2 |
3 |
4 |
5 |
GNM. |
Trækstyrke MPa |
18,72 |
19,45 |
19,33 |
19,64 |
19,70 |
19,36 |
- Tværretning |
|
|
|
|
|
|
Brudforlængelse % |
336 |
384 |
355 |
378 |
403 |
371 |
- Tværretning |
|
|
|
|
|
|
Videre-rivestyrke N/mm - Længderetning |
|
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- Tværretning |
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10 - 50 % forlængelse - Længderetning |
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- Tværretning |
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|
|
I tilfælde af, at der ikke køres efter de fastsatte normer, skal dette anføres under
bemærkninger. analysebetingelserne beskrives.
| Trækstyrke | ISO 527-1 og ISO 527-3 |
| Brudforlængelse | ISO 527-1 og ISO 527-3 |
| Videre-rivestyrke | DIN 53363 10 / 50 % |
| Forlængelse | BS 3924 : 1978 |
Bemærkninger:_________________________________________________
_____________________________________________________________
Dato___14/5-01
Udført af____jo______
Reference:
DS/EN ISO 9001:2000 i 2216
Trækprøvning
Logbog for trækprøveapparat / kunde |
||||||
Ordrenr. |
DP 01106 Clear 97 Elvaloy |
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Kvalitet / Farve |
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|||||
Tykkelse |
400 µm |
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Narv |
|
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Analyseresultater |
1 |
2 |
3 |
4 |
5 |
GNM. |
Trækstyrke MPa |
27,67 |
28,22 |
27,70 |
28,88 |
26,04 |
27,70 |
- Tværretning |
|
|
|
|
|
|
Brudforlængelse % |
329 |
331 |
356 |
347 |
304 |
333 |
- Tværretning |
|
|
|
|
|
|
Videre-rivestyrke N/mm - Længderetning |
|
|
|
|
|
|
- Tværretning |
|
|
|
|
|
|
10 - 50 % forlængelse - Længderetning |
|
|
|
|
|
|
- Tværretning |
|
|
|
|
|
|
I tilfælde af, at der ikke køres efter de fastsatte normer, skal dette anføres under
bemærkninger. analysebetingelserne beskrives.
| Trækstyrke | ISO 527-1 og ISO 527-3 |
| Brudforlængelse | ISO 527-1 og ISO 527-3 |
| Videre-rivestyrke | DIN 53363 10 / 50 % |
| Forlængelse | BS 3924 : 1978 |
Bemærkninger:_________________________________________________
_____________________________________________________________
Dato___14/5-01
Udført af____jo______
Reference:
DS/EN ISO 9001:2000 i 2216