Abordagens de Desenvolvimento e Manufatura de Produtos Biopoliméricos

BioPiT – New Approaches of Product
Development and Manufacturing of

Biopolymers
BioPiT – Biopolymers in Thuringia Slide 1

Projektkonsortium
BioPit
Agenda
1. Introduction
2. Presentation of the Results

1. Chemical and Procedural Basics
2. Modification and Preparation of the Materials
3. Manufacturing Technologies
4. Specific Product Development

Projektkonsortium
BioPit
Aims of the Project BioPiT
 Generation of the scientific and procedural basics for the creation of new
biobased polymers, monomers, additive compounds and addition agents
 Production of the biobased monomers, polymers and addition agents

ideally in Thuringia
 Development of suitable manufacturing technologies, machines and plants

for biobased products

Projektkonsortium
BioPit
Aims of the Project BioPiT
 Highlighting and utilization of the special and unique properties of the

biobased polymers and their use in new products and applications
 Finding new partners for further manufacturing over the whole process
chain
 To determine the markets of biobased polymers, exclusive as well as

substitution of petro-based polymers

Projektkonsortium
BioPit
Project partners of BioPit
TITK FHS
Delivering of the developed Analyzing of the material
addition agents properties
TUI
Deliviering of the delivered
storage module
RMA-TSK
Manufacturing of
demonstration parts
Grafe FHS Feintechnik

Development of a Guideline Developing of a
Integration of the addition for the product develoment biobased razor
agents in masterbatches with biobased polymers due

Projektkonsortium
BioPit
Subprojects of the Project

2. Modification and Preparation of the Materials

Projektkonsortium
BioPit
(TITK)
Functional polymer addition

agents by using herbal
feedstocks as monomer basis

Projektkonsortium
BioPit
Feedstocks and Processes
 Extraction of mixtures of fatty acids (FA) from rape oil (C18) and colewort (C22)
Splitting of thetriglyceride of the rape oil direct esterification C22-FA
Hydrolysis with boric acid

Result:
Esterification
Refining
Refinement
Two biogenic monomers are available for the
Esterification
Direct use
synthesis of the addition agents
Fatty acid alcyl 60% single unsaturated

C22-fatty acid-methyl ester
32% multiple unsaturated
methyl ester 8% saturated
ca. 90% single unsaturated

Projektkonsortium
BioPit
Synthesis of Addition Agents
C18- bzw. C22- derivates of fatty acids as basis component for multifunctional addition agents
Integration of a headgroup and an anchor segment as carrier of important material properties
Headgroup + C18 / C22 + Anchor segment

Result:
Light protection Matrix
Biocide Multi functionality of the addition agents
PA can compatibility
PE
Ox./Therm.Stab. be formulated by combination of the PLA
Homogenization
monomers.
Multifunctional addition agents

Labor-parallel-Reaktor

Projektkonsortium
BioPit
Synthesis of Addition Agents, Analytics and
Variable Fuctions
Built up Monomers Analytics
Result:
Adaption of functions and additiv structures to

various polymers is possible (compatibility of
matrix)

Projektkonsortium
BioPit
Processing, Test Bodies, Characterization
Test materials have been processed (compounding, injection molding)
• Biocide (PA 6, 6.6)
• Light protection (PA 6)
• chem. stabilizer (PA 6, 6.6; PLA)
• thermal, oxidative stabilizer (PA 6, PLA?)
I.E.: biocide addition agents
Preparation of the herbal oils

Separation of the glycerides Derivatization
Synthesis of the addition agents
F 2,6
Compoundiing Processing Antibacterial Effectivity in PA 6

(Staphylococcus aureus)

Projektkonsortium
BioPit
Processing, Test Bodies, Characterization
Test materials have been processed (compounding, injection molding)
• Biocide (PA 6, 6.6)
• Light protection (PA 6)
• chem. stabilizer (PA 6, 6.6; PLA)
• thermal, oxidative stabilizer (PA 6, PLA?)
I.E.: UV-absorbing addition agent

Result:
Thermoplastic processing of most addition

Preparation of the herbal oils
agents isaddition
possible (Compounding,
Separation of the glycerides Derivatization
Synthesis of the agents
Masterbatches, Extrusion…)
TINUVIN 234 pure
UV-protection, biobased add. agent
Adjustment between addition agent and

polymer matrix is necessary.
Compoundiing Processing UV-Absorption

Projektkonsortium
BioPit
Conclusion
 Extraction of two basis monomers from herbal feedstocks
(Fatty acids and derivates C22 and C18)
 Combination with other substances leads to functional addition agents
 Proved properties: antibacterial Effectivity

thermal stabilization
UV protection
flexibilizer
 Test materials can be processed thermoplastically (compounding)
 In application an adjustment of the addition agents to the polymer matrix

is necessary

Projektkonsortium
BioPit
2. Modification and Preparation of the
Materials (Grafe)
BIOSELECT

Projektkonsortium
BioPit
Black Mulch foils
Advantage
 cheap (ca. 0,10 € / m²)
Disadvantage
 Pigmented with carbon black
 Impervious to UV-light, light and heat
 Absorbs the heat radiation
 Heats itself
 Passes the heat in all directions

Projektkonsortium
BioPit
Advantages of IRT (Infrared transparent)
Pigents –„Agri Black®“
 Dark color allow:

 Higher absorption of UV-light and light
 Higher Temperatures in the dam
 High transmission of heat (NIR) – heat can pass the foil

Projektkonsortium
BioPit
Pictures of a heat image camera
(Source: RKW Michelstadt (2012))
Carbon black foil Grafe IRT foil

Projektkonsortium
BioPit
Requests to a bio-degradable Foil containing IRT-
Pigments
 Photo selective mulch foil

 Basis: PLA (Polylactic acid)
 Not so susceptible to moisture as cellulose based bio-degradable polymers
 Cultivation of fruits or vegetables in a dam
 Worms and voles are expelled
 Other plants (weed) is prevented – herbcides are not necessary
 Within 90 day in industrial compost: >90% of the foil mass must be
dissipated by bacteria

Projektkonsortium
BioPit
Tests done by LVG Erfurt
 Standard LDPE Mulch foil (V1)

 LDPE Agri Black Grafe (V2)
 Mater-Bi Agri Black Grafe (V3)
 Bioflex Agri Black Grafe (V4)
 Ecovio / Ecoflex (BASF) not possible

Projektkonsortium
BioPit
Gerkhins

Projektkonsortium
BioPit
LVG Erfurt: Gerkhins
Weight dependent on Foil type
Gerkhins in 2012
Harvest weight in kg

Projektkonsortium
BioPit
Tomatoes

Projektkonsortium
BioPit
Tests done by LVG-Erfurt
 V1 - PE without problems
 V2 – Agri Black Grafe

LDPE without problems
 V3 – Mater-Bi Agri Black

Damages at the border of
the foil, frayed, color
changed to blue, foil was
no longer fixed
 V4 – Bioflex Agri Black

some smaller unruffled
holes, foil is fixed stable
on the area

Projektkonsortium
BioPit
LVG Erfurt: Tomatoe Test
Harvests (kg) acc. to Foil Type
Tomatoe project 2012
Harvests in kg
Harvests (kg)
Green fruits
Not salable
Salable

Projektkonsortium
BioPit
LVG Erfurt: Tomatoe Test
Harvests (kg) acc. to bed form
Tomatoe project 2012
Harvests in kg
Harvests (kg)
Green fruits
Not salable
Salable
dam bed

Projektkonsortium
BioPit
Tests done by MFPA Weimar
 Analyzing of the bio-

degrabability
according to DIN EN
ISO 14855-1
 Ecological toxicity
according to DIN EN
13432

Projektkonsortium
BioPit
Release of CO2
 LDPE 15,1 % CO2
 Bioflex (FKuR) 92,2 % CO2
 Mater-Bi (Novamont) 90,5% CO2
 Required bio-degradability of over 90 % is reached according to DIN EN

ISO 14855-1.
 Test duration: September to Dezember 2012 (14 Weeks)

Projektkonsortium
BioPit
Conclusion
 Required bio-degradability of over 90 % is reached according to DIN EN

ISO 14855-1
 The ecological toxicity test was passed.
 From processing aspects: Bioflex F 1130 from FKuR (MFR=3 g/10 min at
190°C/2,16 kg, Density 1,4g/cm³)

Projektkonsortium
BioPit
(TU Ilmenau & RMA-TSK)

Projektkonsortium
BioPit
Challenges when Processing Biobased Polymers by
Injection Molding
Specification Sheet for Technical Parts in
Automotive Industry
 Loss of molecular weight up to 50 % when
using conventional processing procedures Funcion
 Minimizing of the thermal and mechanical Creation of an average room temperature 22-28°C
stress during processing max. air-mass throughput 5-12kg/min
Temperature at the air outlet die max. 70°C (Winter)
min. -2°C (Summer)
Structure
Tension Modulus of elasticity 3.250 MPa
Break stress 23 MPa
Breaking strain 16%
Charpy impact energy (23°C) 3 kJ/m²
Heat deflection temperature (HDT-A-1,8) 69°C
Gogolewski, S.: The Effect of Melt-Processing on the Degradation of selected Parts: Body of an air conditioning unit (Fa. RMA/ TSK)
Polyhdroxyacids: PLA, PHB and PHB-co-HV

Projektkonsortium
BioPit
Comparative Processing of Biobased Polymers (PLA,
CA, PHBV) with different Injection Molding Machines
Prägewerkzeug
TUI TUI TUI RMA/ TSK KraussMaffei RMA/ TSK

ILC 1000to
Rohmaterial
werkzeug
Standard-
Standard-
maschine
maschine
ILC 1000t
ILC 200t
Präge-
650t
60t
Umbau ISS - -
Prüf-
Musterteil Musterteil Musterteil Herstellungsverfahren
werkzeug
5 5 5 3 3 3 Materialien
- + + + + + Massetemperatur
parameter
- + + + + + Verweilzeit
Prozess-
- - + + + + Einspritzgeschwindigkeit
-
-
-
-
+
+
+
+
+
+
+
+
Nachdruck
Umfangsgeschwindigkeit
SGM 650to
Kombinations-
möglichkeiten
- + + + + + Massetemperatur/Verweilzeit
- - + + + + Verweilzeit/Einspritzgeschw.
- - + + + + Einspritzgeschw./Nachdruck
- - + + + + Nachdruck/Umfangsgeschw.
- + + + + + Zugversuch
Materialprüfung
+ + + + + + DSC
- + + + + + Kerbschlag
- + + + + + HDT/Vicat
+ - - - - - HDKR
+ - - - - - GPC
+ - - - - - MFI
ILC 200to thermal and shearing stress SGM 60to

Projektkonsortium
BioPit
The process affects the Properties
Screw speed Dwell time Injection rate Filling pressure Temperature
SGM 60t
Screw speed Dwell time Injection rate Temperature
SGM 650t
Screw speed Filling pressure Injection rate Temperature
ILC 200t

Projektkonsortium
BioPit
Optimization of the Properties of the Part by Improving
the Process
 Selection of Molding tool and Machine can not be compared to conventional plastics
 Selective Optimization of the Process necessary
 Material specific processing necessary
% Tension stress
PLA CA PHBV % Tension strain
% Youngs
Modulus
PLA CA PHBV
SGM 60t SGM 650t ILC 200t SGM 60t SGM 650t ILC 200t SGM 60t SGM 650t ILC 200t
Process conditions
Verarbeitungsbedingungen
Injection speed
Einspritzgeschwindigkeit o -- -- -- -- -- -- -- o
Filling pressure
Nachdruck ++ ++ ++ ++ ++ -- -- -- -
Dwell time
Verweilzeit -- o o o -- o -- o o
Peripherrical speed
Umfangsgeschwindigkeit o ++ o o -- o -- -- --
Mass temperature
Massetemperatur o -- + -- -- ++ + o --
-- geringer Einfluss '+ großer Einfluss o vernachlässigbarer Einfluss
Projektkonsortium
BioPit
Development of a machine concept to process biobased
polymers gently (patent application)
 First-In First-Out: no mixture of melt having different
dwell times
 Continous plastification during the whole cycle
 Reduction of dwell time and shear stress
 Little fluctuation of pressure and temperature for a
stable cycle
 In-Line processing, reduction of the value added chain
Schmelzezufuhr
Overflow Storage Extruder
channel room
Injection room Ring piston

(Relative movement)
Projektkonsortium
BioPit
(UoAPS Schmalkalden & Feintechnik Eisfeld)

Projektkonsortium
BioPit
Product Development acc. to VDI 2221
[Pahl, Beitz]

Projektkonsortium
BioPit
Simulation of the Filling Process
 Simulation of the Injection Molding Process
 Important Instrument in Product Development

 Balanced filling
 Balancing of the runner
 Reducing of the clamp force
 Optimization of the position of weld lines
 Optimization of melt flow
 Optimization of cycle time
 Optimization of warpage
 Identification of defects

Projektkonsortium
BioPit
Deficits of the Available Data on the part of the
Material Producers
Available Data:
• Melting Temperature
• Process Window
• Melt Flow Rate
• Hardness
• Modulus of Elasticity
Missing Data:
• Viscosity data
• p-v-T-Data
• Specific
heat capacity
• Poisson ratio
• Modulus of Shear

Projektkonsortium
BioPit
Tested Materials of Feintechnik Eisfeld
 Polylactid-Compounds, Fa. FKuR, Willich (D)

 S 5630
 S 1100
 Cellulose-Acetate (CA), Fa. FKuR, Willich (D)

 C 7500
 Polyethylen (Bio-PE), Fa. Braskem, Sao Paolo (Bra)

 SHA 7260
 Polyamide (Bio-PA), Fa. DuPont, Wilmington (USA)

 Zytel RS LC3060 NC010

Projektkonsortium
BioPit
What do we need to do a filling simulation?
Filler
Properties
Material Mechanical
Description Data
Recommended p-v-T-Data
Processing
Rheological Thermal Data

Data

Projektkonsortium
BioPit
Experimental Design
Rheology
Thermal p-v-T-Data Manifacturing of Mechanical
Analyses Thermal Test Bodies Properties
Conductivity

Projektkonsortium
BioPit
Material Description
exemplary: SHA 7260
Parameter Value
Familiy name Polyethylen
Tradename SHA 7260
Manufacturer Braskem
Family Abbreviation PE
Material structure Crystalline
Fibers/Fillers unfilled

Projektkonsortium
BioPit
Recommended Processing
exemplary: SHA 7260
Result:
The melting area of the semi-crystalline SHA

7260 is between 105 °C and 150 °C.
Semicrystalline material
Second heating:
Tm = 135 °C ± 0,5 °C
Projektkonsortium
BioPit
Recommended Processing
exemplary: SHA 7260
Default values
Mold surface Temperature 30 °C
Melt temperature 170 °C
Mold temperature (recommended)

Minimum 20 °C
Maximum 40 °C
Melt temperature (recommended)

Minimum 150 °C
Maximum 220 °C
General values
Absolute maximum melt temperature 250 °C
Ejection temperature °C
Maximum shrear stress MPa

Maximum shrear rate 1/s
Melt mass flow rate (optional)

Projektkonsortium
BioPit
Rheological Data
exemplary: SHA 7260
aT 0
    1 n
    
1  aT   0 * 
  
Log Viskosity [pa s]
Newtonian Flow behavior
Shear Thinning Flow behavior

[Menges, Haberstroh]
Log Shear rate [1/s]

Projektkonsortium
BioPit
Rheological Data
exemplary: SHA 7260
aT 0
1000     1 n
    
1  aT   0 * 
Viscosity η [Pa s]
  
100 Result:
Mathematic flow models can be used for

standard plastics and for biobased plastics!
[Menges, Haberstroh]
10
50 500 5000
Shear rate γ' [1/s]
200 °C 195 °C 190 °C 185 °C 180°C 175 °C 170 °C

Projektkonsortium
BioPit
Specific Heat Capacity
exemplary: SHA 7260
20
18
Spefific Heat Capacits cp
16
14
[kJ/(kg K)]
12
10
8
6
4
2
0
50 60 70 80 90 100 110 120 130 140 150 160
Temperature Θ [°C]

Projektkonsortium
BioPit
Thermal Conductivity
exemplary: SHA 7260
0,275
0,27
Thermal Conductivity λ
0,265
0,26
[W/(m K)]
0,255
0,25
0,245
0,24
0,235
150 155 160 165 170 175 180 185 190

Projektkonsortium
BioPit
Thermal Data
exemplary: SHA 7260
Temperature Specific heat Temperature Thermal

[°C] Capacity [°C] Conductivity
[J/(kg K)] [W/(m K)]
60 2,189 190 0,285
70 2,315 180 0,285
80 2,481 170 0,245
90 2,72 160 0,243
100 3,098 150 0,237
110 3,707
120 5,172
130 12,424
140 3,536
150 2,653
160 2,616
Projektkonsortium
BioPit
p-v-T-Data
exemplary: SHA 7260
Specific volume v
Temperature T

Projektkonsortium
BioPit
p-v-T-Data
exemplary: SHA 7260
1,4
specific Volume v [cm³/g]
1,35
1,3
1,25
Result:
1,2
1,15 Tait-Equation can be used for standard plastics
and also for biobased plastics!
1,1
1,05
1
70 90 110 130 150 170 190 210

Projektkonsortium
BioPit
Mechanical Data
exemplary: SHA 7260
Parameter Symbol Value Unit

Elastic modulus, 1st principal direction E1 870 MPa
Elastic modulus, 2nd principal direction E2 870 MPa
Poissons ratio ν12 0,448
Poissons ratio ν23 0,448
Shear modulus G12 300 MPa

Projektkonsortium
BioPit
Conclusion
Analyses of the Biobased Plastics
 Identification of Melting Temperatures/Glass Transition Temperatures

 Analyzing of the thermal Behavior with DSC and TGA
 Result: The process temperatures are not allways in the range of the
given values from the data sheet
 Identification of the physical Behavior

 Analyzing of the Viscosity Behavior
 Analyzing of the p-v-T Behavior
 Result: Analyzed Materials behave as Standard Plastics in General

 Mathematic models can be used

Projektkonsortium
BioPit
Practical Application:
The Biobased Razor

Projektkonsortium
BioPit
Material Selection of the Biobased Razor
Part Hard Component Soft Component

Projektkonsortium
BioPit
Colours of the Biobased Razor

Projektkonsortium
BioPit
Biobased Package

Projektkonsortium
BioPit
Conclusions of the Project
Build up of the Guideline
 Introduction
 Definition of the terms biobased polymer and bioplastic
 Conflicts of command variables when handling bioplastics
 Specific process in product development for bioplastics

 Planning phase
 Conception phase
 Design phase
 Phase of technical preparation
 Process development for bioplastics

 Developing of molding tools
 Manufacturing of bioplastics by injection molding
 Manufacturing of bioplastics by extrusion

Projektkonsortium
BioPit
Conclusions of the Project
Reaching of the Aims
 Generation of the scientific and procedural basics for the creation of new biobased polymers,
monomers, additive compounds and addition agents
 Production of the biobased monomers, polymers and addition agents ideally in Thuringia
 Development of suitable manufacturingResult:

technologies, machines and plants for biobased
products
The aims could be reached as far as possible.
 Highlighting and utilization of the special and unique properties of the biobased polymers and
their use in new products and applications
 Finding new partners for further manufacturing over the whole process chain
 To determine the markets of biobased polymers, exclusive as well as substitution of petro-

based polymers

Projektkonsortium
BioPit

Abordagens de Desenvolvimento e Manufatura de Produtos Biopoliméricos

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Abordagens de Desenvolvimento e Manufatura de Produtos Biopoliméricos

Uploaded by

Copyright:

Available Formats

BioPiT – New Approaches of Product

Development and Manufacturing of

BioPiT – Biopolymers in Thuringia Slide 1

2. Presentation of the Results

BioPiT – Biopolymers in Thuringia Slide 2

 Production of the biobased monomers, polymers and addition agents

 Development of suitable manufacturing technologies, machines and plants

BioPiT – Biopolymers in Thuringia Slide 3

 Highlighting and utilization of the special and unique properties of the

 To determine the markets of biobased polymers, exclusive as well as

BioPiT – Biopolymers in Thuringia Slide 4

Grafe FHS Feintechnik

BioPiT – Biopolymers in Thuringia Slide 5

1. Chemical and Procedural Basics

BioPiT – Biopolymers in Thuringia Slide 6

Functional polymer addition

BioPiT – Biopolymers in Thuringia Slide 7

Splitting of thetriglyceride of the rape oil direct esterification C22-FA

Hydrolysis with boric acid

synthesis of the addition agents

Fatty acid alcyl 60% single unsaturated

BioPiT – Biopolymers in Thuringia Slide 8

Headgroup + C18 / C22 + Anchor segment

Multifunctional addition agents

BioPiT – Biopolymers in Thuringia Slide 9

Adaption of functions and additiv structures to

BioPiT – Biopolymers in Thuringia Slide 10

I.E.: biocide addition agents

Preparation of the herbal oils

Compoundiing Processing Antibacterial Effectivity in PA 6

BioPiT – Biopolymers in Thuringia Slide 11

I.E.: UV-absorbing addition agent

Thermoplastic processing of most addition

Adjustment between addition agent and

Compoundiing Processing UV-Absorption

BioPiT – Biopolymers in Thuringia Slide 12

 Combination with other substances leads to functional addition agents

 Proved properties: antibacterial Effectivity

 Test materials can be processed thermoplastically (compounding)

 In application an adjustment of the addition agents to the polymer matrix

BioPiT – Biopolymers in Thuringia Slide 13

BioPiT – Biopolymers in Thuringia Slide 14

BioPiT – Biopolymers in Thuringia Slide 15

 Dark color allow:

BioPiT – Biopolymers in Thuringia Slide 16

Carbon black foil Grafe IRT foil

 Photo selective mulch foil

BioPiT – Biopolymers in Thuringia Slide 18

 Standard LDPE Mulch foil (V1)

 Ecovio / Ecoflex (BASF) not possible

BioPiT – Biopolymers in Thuringia Slide 19

BioPiT – Biopolymers in Thuringia Slide 20

BioPiT – Biopolymers in Thuringia Slide 21

BioPiT – Biopolymers in Thuringia Slide 22

 V2 – Agri Black Grafe

 V3 – Mater-Bi Agri Black

 V4 – Bioflex Agri Black

BioPiT – Biopolymers in Thuringia Slide 23

BioPiT – Biopolymers in Thuringia Slide 24

BioPiT – Biopolymers in Thuringia Slide 25

 Analyzing of the bio-

BioPiT – Biopolymers in Thuringia Slide 26

 LDPE 15,1 % CO2