Methodology for the Selection of Suitable Additives to Reduce Undesirable Odour/VOC from Biocomposite Materials

Transcription

1 13 th Conference Emissions and Odours from Materials October 5-6, 2017 Methodology for the Selection of Suitable Additives to Reduce Undesirable Odour/VOC from Biocomposite Materials Catherine Brasseur Materials - Environment - Process intensification Copyright CERTECH Certech Member of EMRA

2 Research Center in Chemistry

3 Contract research organisation providing support to industries Services Analytical support Problem solving Quality control Regulatory assessment Industrial projects Product/process development Product/process improvement Collaborative projects Competence development Product development Process development

4 Activities ENVIRONMENT Health & safety I Energy Recycling POLYMER MATERIALS TECHNOLOGY Barrier materials (packaging & functional coatings) (Bio-based) polymers & composites Blends & alloys of recyclates PROCESS INTENSIFICATION Continuous processes Catalytic pyrolysis & solvolysis Inorganic & organic synthesis ANALYTICAL SERVICES Characterization, problem solving, method development Chemicals, polymers, building, automotive & transportation, packaging, medical, pharmaceutical & healthcare, environment 38 employees; 3,8 million Euro turnover

5 Odour and Emissions from Materials Consumer awareness has increased : More stringent demands regarding quality life, e.g. comfort, safety Information by public authorities, consumer organisations and health professionals Press coverage Impact of environmental issues : Compliance with legal requirements Compliance with customer requirements (pressure from end-users) Labels and producers awareness Marketing issues (odourless and low VOC grades)

6 Odour and Emissions from Materials Expertise in odour and air sampling for more than 35 years Knowledge of various applications such as: - Food packaging (off-flavour problem solving) - Cosmetic and medical packaging - Consumer products - Transport - Building products - Indoor air quality Automotive OEM and ISO accreditation N 400 TEST Questions from industry, national laboratories, universities Analytical support Problem solving

7 Odour and Emissions from Materials Our methodology Key steps of action 1 - Characterisation of emissions (Chemical and odour analysis, Correlation odour/offflavour) 2 - Identification of the causes (Knowledge of polymer formulation, degradation and Diagnostic migration phenomena) 3 Remediation (Impact of process, formulation, treatments, ) 4 Evaluation (Labels, Schemes, Standards but also Quick and cost effective pre-test)

8 Production of Biocomposites Biocomposite = composite material + reinforcement of natural fibers Hemp Fibers from hemp stem Hemp fibers Raw or retted Accoustic ceiling, Thermal insulation Hemp rope

9 Production of Biocomposites Hemp plastic interior of a car door Hemp plastic automobile glove box Hemp plastic column, automobile

10 Interest of automotive industry for Biocomposites Almost every car manufacturer proposes an ecological label* : Production of Biocomposites Renault Seat BMW Ford Use of biobased / biocomposite materials* : PARTS Lateral Shelf Door Panel Trims Seats (Foam or back seat body shell) Trunk Carpet Central Armrest CAR MANUFACTURER NON EXHAUSTIVE VEHICLES NON EXHAUSTIVE PEUGEOT CITROËN C3 Pluriel, C4, C5, C8, 607, 807 TOYOTA MERCEDES FORD BMW Premium (Prius) Classe A, C, E, S Lincoln MKX, Ford F-150, Super Dusty BMW I3 * ALEXIA ROMA (Groupe Renault); 4E COLLOQUE «FIBRES NATURELLES & POLYMERES»

11 Production of Biocomposites Different grades of hemp: Retted Semi-retted Not retted Compaction Pellets

12 Production of Biocomposites Extrusion (polymer + 20wt% Hemp) Retted / semi-retted / not retted hemp + PP polymer Composites obtained 3 composites : (PP + hemp1) (PP + hemp2) (PP + hemp3)

13 Evaluation of Biocomposites (Odour and VOC) Characterizaton of Odour and VOC emissions I) Conditioning: Static ageing during 2h at 70 C Pellets of : PP PP + hemp 1 PP + hemp 2 PP + hemp 3 II) Sampling of the gas phase: - Tedlar bag for odor testing - Active sampling on sorbent cartridges (Tenax ) for VOCs analysis

14 Evaluation of Biocomposites (Odour and VOC) Characterizaton of Odour and VOC emissions III) Analyses Quantitative analyses of odour by Dynamic dilution olfactometry Quantitative and Qualitative analyses of odour by evaluation using intensity scale and descriptors according to the «champ des odeurs» with expert panels VOC analysis On-line FID Thermal Desorption- GC-MS analysis Accredited method EN Accredited by french OEM (ISO and ISO5496) A B-C D

15 Odour concentration (oue/m³) Evaluation of Biocomposites (Odour and VOC) A. Quantitative analyses of odour by dynamic dilution olfactometry PP/ PP + H1/ PP + H2/ PP + H Polymer PP PP + hemp 1 PP + hemp 2 PP + hemp 3 PP matrix : significantly lower relative odor concentration than the composites PP + hemp 3 composite (not retted fibers): significantly higher relative odour conc. PP + hemp 2 (semi-retted fibers) and PP + hemp 1 (retted fibers): similar odour level

16 Mean intensity Evaluation of Biocomposites (Odour and VOC) B. Quantitative analyses of odour by intensity scale 3,5 3 2,5 2 1,5 1 0,5 0 PP Polymer PP + hemp 1 PP + hemp 2 PP + hemp 3 Average intensities of odour of composites are slightly higher than the PP polymer

17 Intensity Evaluation of Biocomposites (Odour and VOC) C. Qualitative analyses of odour by the «champ des odeurs» methodology 5 4,5 4 3,5 3 2,5 2 1,5 1 0,5 0 Poles Polymer PP PP + hemp 1 PP + hemp 2 PP + hemp 3 Fatty Coumarin Woody Spicy Moldy / earthy Phenol Caramel Roasted Sulfur Pungent Characteristic notes of polymer matrix : fatty, woody, phenol, caramel PP / hemp composites are characterised by a common roasted note The PP / hemp 1 is characterised by a spicy note The PP / hemp 2 is characterised by a coumarin, moldy/earthy, sulfur notes The PP / hemp 3 is characterised by a pungent note The PP / hemp 2 composite appears to be the most unpleasant

18 TVOC (ppm) Evaluation of Biocomposites (Odour and VOC) D. Evaluation of TVOC by on-line FID analysis PP polymer PP + hemp 1 PP + hemp 2 PP + hemp 3 The PP Polymer is less emissive than the composites PP + hemp 3 composite is the most emissive (higher TVOC level) PP + hemp 2 and PP + hemp 1 composites have an intermediate level of emission

19 Evaluation of Biocomposites (Odour and VOC) Criteria for selection of candidate: The hemp 3 (not retted fibers) is far too emissive to be considered by the automotive industry even if more competitive (less costly) PP + hemp 2 and PP + hemp 1 composites demonstrated similar odour intensity and TVOC emissions. But PP + hemp 2 composite is characterised by more unpleasant notes (moldy/earthy, sulfur notes). The hemp 2 (semi-retted fibers) is less expensive than hemp 1 (retted fibers) PP + hemp 2 composite has been selected for the next step

20 Reducing undesirable Odour/VOC emission Comparison of odour remediation additives effect on PP+hemp2 composite selection of 4 additives with different concentrations Matrix (M): PP + hemp 2 M + 0,2 % additive 1 M + 1 % additive 1 M + 1 % additive 2 M + 2 % additive 2 M + 0,5 % additive 3 M + 1 % additive 3 M + 1 % additive 4

21 Odour concentration (oue/m³) Reducing undesirable Odour/VOC emission A. Quantitative analyses of odour by dynamic dilution olfactometry PP + hemp 2 (M) M + 0,2 % additive 1 M + 1 % additive 1 M + 1 % additive 2 M + 2 % additive 2 A difference between olfactometry results is considered as significant when at least a factor 2 is observed between 2 evaluations

22 Odour concentration (oue/m³) Reducing undesirable Odour/VOC emission A. Quantitative analyses of odour by dynamic dilution olfactometry PP + hemp 2 (M) M + 0,5 % additive 3 M + 1 % additive 3 M + 1 % additive 4 A difference between olfactometric results is considered as significant when at least a factor 2 is observed between 2 evaluations The additive 3 appears to be the most active at this stage

23 Mean intensity Reducing undesirable Odour/VOC emission B. Quantitative analyses of odour by intensity scale 3,5 3 2,5 OEM Specifications 2 1,5 1 0,5 0 PP + hemp 2 (M) M + 0,2 % additive 1 M + 1 % additive 1 M + 1 % additive 2 M + 2 % additive 2 The biocomposite + Additive 2 (2%) is a candidate to meet OEM specifications

24 Reducing undesirable Odour/VOC emission B. Quantitative analyses of odour by intensity scale 3,5 3 2,5 OEM Specifications 2 1,5 1 0,5 0 PP + hemp 2 (M) M + 0,5 % additive 3 M + 1 % additive 3 M + 1 % additive 4 The biocomposite + additive 3 (1%) is a candidate to meet OEM specifications

25 Intensity Reducing undesirable Odour/VOC emission C. Qualitative analyses of odour by the «champ des odeurs» methodology 3 2,5 PP + hemp 2 (M) M + 0,5 % additive 3 M + 1 % additive 3 2 1,5 1 0,5 0 Fatty Amine Coumarin Woody Moldy / earthy Phenol Roasted Poles The additive 3 decreases the fatty, moldy/earthy and roasted notes The additive 3 (1%) is selected in terms of odour reduction

26 Reducing undesirable Odour/VOC emission To study the reduction of undesirable odour from PP/hemp composites, some additives with different actions mode are added to the formulations Methodology M + 0,2 % additive 1 M + 1 % additive 1 M + 1 % additive 2 M + 2 % additive 2 M + 0,5 % additive 3 M + 1 % additive 3 M + 1 % additive 4 A. Quantitative odour analyses (dynamic olfactometry) B. Quantitative odour analysis (intensity) C. Qualitative odour analyses (descriptors) The additive 3 has a positive impact on the biocomposite global odour reduction and the removal of unpleasant notes (roasted, fatty, amine, moldy/earthy)

27 Reducing undesirable Odour/VOC emission Comparison of odour remediation additives effect on PP+hemp2 composite Confirmation of the results obtained with additive 3 + Selection of 5 additional additives with different concentrations Matrix (M): PP + hemp 2 M+1 % additive 3 M+2% additive 5 M+1% additive 6 M+5% additive 6 M+2% additive 7 M+2% additive 8 M+0,2% additive 9 M+1% additive 9

28 Odour concentration (oue/m³) Reducing undesirable Odour/VOC emission A. Quantitative analyses of odour by dynamic dilution olfactometry Reference (PP+ hemp 2 = M) 708X019 M+1% additive 3 708X018 M+2% additive 5 708X020 M+1% additive 6 708X021 M+5% additive 6 Confirmation that the biocomposite + 1% additive 3 has significantly lower odor concentration than the matrix (PP + hemp 2) PP + hemp 2 + 5% additive 6 shows the lowest odour level.

29 Odour concentration (oue/m³ Reducing undesirable Odour/VOC emission A. Quantitative analyses of odour by dynamic dilution olfactometry Reference (PP+ hemp 2 = M) 708X022 M+2% additive 7 708X023 M+2% additive 8 708X024 M+0,2% additive 9 708X025 M+1% additive 9 No significant difference observed with the others additives tested

30 Global odour intensity Reducing undesirable Odour/VOC emission B. Quantitative analyses of odour by intensity scale 3,5 3 2,5 OEM Specifications 2 1,5 1 0,5 0 Reference (PP+ hemp 2 = M) 708X019 M+1% additive 3 708X018 M+2% additive 5 708X020 M+1% additive 6 708X021 M+5% additive 6 Confirmation that the biocomposite + Additive 3 could meet the OEM specifications No confirmation of a low intensity level for PP + hemp 2 + 5% additive 6 (compared to dynamic olfactometry results)

31 Global odour intensity Reducing undesirable Odour/VOC emission B. Quantitative analyses of odour by intensity scale 3,5 3 2,5 2 1,5 1 0,5 OEM Specifications 0 Reference (PP+ hemp 2 = M) 708X022 M+2% additive 7 708X023 M+2% additive 8 708X024 M+0,2% additive 9 708X025 M+1% additive 9 The biocomposite + Additive 7 or additive 8 could meet the OEM specifications

32 Intensity Intensity Reducing undesirable Odour/VOC emission C. Qualitative analyses of odour by the «champ des odeurs» methodology 3 2,5 2 1,5 1 0,5 PP + hemp 2 (M) M + 0,5 % additive 3 M + 1 % additive 3 0 Poles Fatty Amine Coumarin Woody Moldy / earthy Phenol Roasted Confirmation that the additive 3 decreases the fatty and roasted notes Poles 3 2,5 2 1,5 1 0,5 0 PP + hemp 2 (M) B M + 1% additive 3 B Fatty Coumarin Woody Moldy / earthy Roasted

33 Intensity Reducing undesirable Odour/VOC emission C. Qualitative analyses of odour by the «champ des odeurs» methodology 3 PP + hemp 2 (M) M + 5% additive 6 2,5 2 1,5 1 0,5 0 Poles Fatty Coumarin Woody Moldy / earthy Roasted The biocomposite + 5% additive 6 presented a significant roasted note

34 Relative Odour Concentration (%) Reducing undesirable Odour/VOC emission SUMMARY of dynamic dilution olfactometry results 140 PP + hemp 2 (M) M + 1% additive 3 M + 5% additive Experiment 1 Experiment 2

35 Relative TVOC amount (%) Reducing undesirable Odour/VOC emission D. VOC analysis by TD-GC-MS 140 PP + hemp 2 (M) M + 1% additive Experiment 1 Experiment 2 TVOC ISO

36 Reducing undesirable Odour/VOC emission D. VOC analysis by TD-GC-MS Experiment 1 PP + Hemp2 (M) M + 1% Additive 3

37 Reducing undesirable Odour/VOC emission D. VOC analysis by TD-GC-MS Experiment 1 M + 1% Additive 3 Heptane 2,2,4,6,6,pentamethyl PP + Hemp2 (M)

38 Reducing undesirable Odour/VOC emission D. VOC analysis by TD-GC-MS Experiment 2 PP + Hemp2 (M) M + 1% Additive 3

39 Reducing undesirable Odour/VOC emission D. VOC analysis by TD-GC-MS Experiment 2 PP + Hemp2 (M) M + 1% Additive 3 Heptane 2,2,4,6,6,pentamethyl Opposite results obtained

40 Reducing undesirable Odour/VOC emission D. VOC analysis by TD-GC-MS Experiment 2 PP + Hemp2 (M) M + 1% Additive 3 ZOOM

41 Reducing undesirable Odour/VOC emission D. VOC analysis by TD-GC-MS Experiment 1 Experiment 2 M + 1% Additive 3 PP + Hemp2 (M) Pentanal PP + Hemp2 (M) Pentanal M + 1% Additive 3 Pentanal = Fresh note

42 Reducing undesirable Odour/VOC emission D. VOC analysis by TD-GC-MS Experiment 1 Experiment 2 Hexanal PP + Hemp2 (M) M + 1% Additive 3 PP + Hemp2 (M) Hexanal M + 1% Additive 3 Hexanal = Fresh note

43 Reducing undesirable Odour/VOC emission D. VOC analysis by TD-GC-MS How to compare 2 samples? ZOOM

44 Reducing undesirable Odour/VOC emission Comprehensive analysis of complex samples and VOC profiles GC GC-TOFMS analysis and data processing GC GC-TOF High Resolution MS (identification of unknowns) 2 t R (sec) 4 2 Capability available at Certech in 2018 (Demo2 Factory Project) t R (min) 2D chromatogram plot provides visual information, very interesting for sample comparison

45 Relative TVOC amount (%) Reducing undesirable Odour/VOC emission D. VOC analysis by TD-GC-MS 140 PP + hemp 2 (M) M + 1% additive 3 M + 5% additive Experiment 1 Experiment 2 TVOC ISO

46 Reducing undesirable Odour/VOC emission D. VOC analysis by TD-GC-MS Experiment 2 PP + Hemp2 (M) M + 5% Additive 6 Significant reduction of VOC emission

47 Conclusions Interest for Formulation and Process development for Biocomposites Methodology for characterization of Odour and VOC emissions - Dynamic dilution olfactometry - Intensity scale - «Champ des odeurs» with expert panels - TD-GC-MS Selection of suitable additives for reduction odor and VOC emissions (Additive 3 + confirmation for additive 6) Promising results obtained, extending possibilities and applications, especially for biobased or recycled materials

48 Acknowledgements Certech Team Tiphaine Pacary Pierre Le Maitre Marie Demeyer Vincent Clause Emmanuel Novak Stéphane Denis

49 Thank you! -