Download - Uwe Stenglin - SINTEF
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
PlasticTechnologieService Marketing- & Vertriebs GmbH
Hautschenmühle 3D 91587 Adelshofen/TauberzellFon +49 (0)9865-821Fax +49 (0)[email protected]
Uwe Stenglin
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Crosslinking of "LIFE PARTS" with
V-PTS-CREAMID PA6, PA6.6 MF/GF
Evaluation of UL-508 standard concerning
Industrial Control Equipment
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
THE STEP OUT OF THE NICHECROSSLINKING
of molded parts, tubes and profiles
withPA6, PA6.6, PA11, PA12 and PBT
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
rays are carriers for energy
the radiation of products cannot -for physical reasons-generate any radioactivity in the product
irradiated products do not emit any radiation itself
the properties of irradiated products are optimized by the energy input -chemical reactions will be caused
this chemical reactions will cause crosslinking or degradation of polymers or sterilization
BGSBETA-GAMMA-SERVICE
WhatWhat areare Rays ?Rays ?
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Gamma-Rays
Radioactive Material (Co-60)
Generation of rays
BGSBETA-GAMMA-SERVICE
Accelerated electrons( beta rays/ e-beams )
like: - TV-Sreens- Röntgen rays
Braun tube
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
3.0MeV-Electron-acceleraterScanner
Tank with SF6
BGSBETA-GAMMA-SERVICE
Generation of rays
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Handlingsystem for Material on reels
BGSBETA-GAMMA-SERVICE
Casset systems for Tubes, pieces and Cartons
Conveyersystems forCartonage and single pieces
Palett-systemsPrinciple of a gamma radiation plant
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Beltsystem for Cartons
BGSBETA-GAMMA-SERVICE
Copyright, 2005 © PTS-Marketing GmbH, TauberzellBGS
BETA-GAMMA-SERVICE
Conveyor system for cartons and bulk productsHandling system for tumbled goods
12000 x 1600mm
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
AmorphousThermoplast
CrystallinThermoplast
ThermoplasticElastomer
PS SAN
PVC
PP
PETPV
TPS TPO
COC PC
PMMAABS
PI
PEI
PES
PEEK
FP
LCPPPS
PA46PA66 PA6 PA11 PA12
PBT PET
TPA
TPU
TPCPMP
Elas
tom
ere
Classification of Thermoplastic Resins
„UPGRADING“BY
CROSSLINKING
HIGH PERFORMANCE
PLASTICS(HDT > 150°C)
ENGINEERINGPLASTICS
(HDT = 100°C–150°C)
STANDARDPLASTICS
(HDT < 100°C)
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
.... mechanical Properties
.... thermal Properties
.... chemical Properties
…. electrical Properties
…. tribological Properties
Improvement of ....(thermoplastic resins)
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
UL 94 - Proceeding for V-PTS-CREAMID (crosslinked)
1. V-PTS CREAMID PA6.6 incl. crosslinking additives and stabilizers
2. Injection moulding conform to PTS standards
3. Crosslinking process under authority of PTSGel content in solving tests min. 60%
4. V-PTS-CREAMID UL-File E173999 approved
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Gel content as a function of the radiation dose (β)
6% BETALINK IC/W 65 PA6
4% BETALINK IC/W 65 PA6
3% BETALINK IC/W 65 PA6
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Control of Heat Distorsion Temperature for crosslinkedparts by soldering test
BGSBETA-GAMMA-SERVICE
Part: PA 6 GF30 Soldering pin: Ø 1mm, weight: 1000g, Temperature: 350°C
Not crosslinked crosslinked
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Thermal Analysis (Differential Scanning Calorimetry) of PA6
The crystallinity is disturbed by the crosslinked areas. The result is a lower crystallisation temperature and reduction of heat content!
HEA
T FL
OW
[W/g
]en
do
TEMPERATURE [°C]
Crystallisation Cooling
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
The trend-setting test in the year 1987
Not crosslinked crosslinked
Parameter:
Time: 15 min
Temperature: 270°C
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
This resins are situated between Technical Thermoplastics and Thermoplastic Elastomers.
Crosslinkable Compounds for the production of tubes are now available!
-50 0 50 100 150 200 250 300 350 400100
101
102
103
104
105
niedriger Vernetzungsgrad
hoher Vernetzungsgrad
Vergleich des Schubmoduls von PA6/PA6.6/PA12 vernetzt / unvernetzt
MPa
°C
PTS-CREAMID A3H2G6 (PA6.6 GF30) PTS-CREAMID B3H2G6 (PA6 GF30) PA12 GF30 V-PTS-CREAMID B3H2G6 (PA6 GF30) vernetzt V-PTS-CREAMID A3H2G6 (PA6.6 GF30) vernetzt PA12 GF30 vernetzt
Sch
ubm
odul
Temperatur
Crosslinking of PA11 and PA12
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Temperature 23°CBurst
pressure not XL
Burst pressure XL
gain
AESN P202T6L 28 33,7 20,4AESN P40 TL 25 32,8 31,2BESN P20 TL 28 38,6 37,9BESN P40 TL 24 28,8 20
Temperature 130°CBurst
pressure not XL
Burst pressure XL
gain
AESN P202T6L 7,5 9 20AESN P40 TL 7 9,2 31,4BESN P20 TL 9 12,3 36,7BESN P40 TL 7,5 10,3 37,3
Temperature 160°CBurst
pressure not XL
Burst pressure XL
gain
AESN P202T6L 0 5,3 >>AESN P40 TL 0 3,8 >>BESN P20 TL 0 6,6 >>BESN P40 TL 0 5,6 >>
Best results at 20% content of plasticizer:
Higher burst pressure of about 40% !
Burst pressure (Mpa) of tubes (8mm*6mm) at different temperatures
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
0 50 100 150 200 2500
20
40
60
80
100
120
140
160
180
200
°C
bar
Versuche an Rohren mit 6mm Außendurchmesser
Ber
stdr
uck
Temperatur
PA11 unvernetzt PA11 vernetzt
Temperature
Bur
stPr
essu
re
Pipes with outer diameter of 6mm
Not crosslinkedcrosslinked
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Crosslinked PA11 and PA12 (RILSAN-based) has no thermoplastic behaviour after the irradiation process.
As a result following properties are characterizing the products:
1.) no surface melting at short thermal peaks above the former melting point
2.) moulded parts and tubes show a Memory-effect
3.) tremendous reduction of thermo fixing times
4.) better dimensional stability of thermo fixed tubes
5.) improvement of the pull-off force of pressed-on tubes
6.) significantly lower creep behaviour
7.) massive improvement of chemical resistance
Crosslinking of PA11 and PA12
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Radiation cross-linked fuel lines and hot water tubing, radiation cross-linked electrical insulation
Technical Applications - Fuel Lines And Hot Water Tubing
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
PTSPTS--GAMMAFLEX E7000/43.1*800GAMMAFLEX E7000/43.1*800
20 40 60 80 100 120 140 1600
25
50
75
100%
°C
PTS-GAMMAFLEX E7000/43.1* vernetzt PTS-GAMMAFLEX E7000/43.1* unvernetzt
DVR
TemperaturTemperature
Com
pres
sion
set
Not crosslinkedcrosslinked
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
PTS-GAMMAFLEX
TPE-X
Simultaneous crosslinking of PA6.6 GF and TPE-X
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
v/m - 170° C
0100200300400500600700800900
1000110012001300
0 2000 4000 6000 8000 10000
Exposed Hrs
v/m
V-PTS-CREAMID-AG7FRPHBASF ULTRAMID A3X2G5V-PTS-CREAMID-A3H2G5V-PTS-CREAMON-A3H2K8
V-PTS-CREAMID-A3H2G5:10-times higher life time as competitor material!
50% line ofstarting conditions
787 h7900 h
Insulation properties in comparison to Ultramid A3X2G5
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Advantages of crosslinked V-PTS-Creamid
Very strong increase of ageing behaviour (RTI-elec.)
RTI (elec.): 150°C in case of V-PTS-CREAMID-GF and MF
RTI (elec.): 140°C in case of V-PTS-CREAMID-FRPH...(red phosphor)
RTI (elec.): 115°C in case of ULTRAMID-A3X2G5
No melting of contacts at T > 258°C
Extreme low flammability (HWI = 0-1), UL can be done without flame retardant
Best quality of contact, because material is free of phosphor and halogens
No limitation in colouring
Low density of flue gas and low toxicity in fire emergency
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Successful unleaded soldering technology at temperatures of 280°C. Replacement of LCP and thermosets in many cases.
High temperature soldering at 450-500°C / 0,5 s feasible
Price reduction of 30% with V-PTS Creamid in comparison to thermosets
Reduction of claims (melted relay carriers down to 0)
No claims caused by thermoset tails (contamination between contacts)
Increase of abrasion resistance
Higher thermal load possible (RTIelectric = 150°C)
Best contact quality (no red phosphorous or halogens)
excellent HWI of 0-1 (Hot Wire Ignition Index)
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Test equipment for HWI (schematic):
6,35mm
SampleV
Power supply: 0,26 W/mm
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
HWI (Hot Wire Ignition – UL-746A) in accordance to ASTM D 3874-88
Goal: Performance level for resistance against ignition of plastic materials caused by an electrical heated wire. The time for ignition defines the PLC value.
Ignition time IT [s] PLC(performance level category)
120 ≤ IT 060 ≤ IT < 120 1
30 ≤ IT < 60 2
15 ≤ IT < 30 3
7 ≤ IT < 15 4
0 ≤ IT < 7 5
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Improvement of short time thermal application limit
TEMPERATURE [°C]
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
V-PTS-CREAMID-A3H2G7
PA66-GF 35
Crosslinked with 100 KGy
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
V-PTS-CREAMON-A3H2K8 for low warpage housing
PA66-MF 40
Crosslinked with 100 KGy
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
V-PTS-CREATEC-B3HG7ZB
PBT-GF 35 impact modified
Crosslinked with 150 KGy
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Creeping behaviour
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Mechanical Properties – Tensile Test in accordance to DIN ISO 527-1
Crosslinking leads to higher tensile strength and reduced elasticity.
TEN
SIO
N [N
/mm
²]
TEN
SIO
N [N
/mm
²]ELONGATION [%] ELONGATION [%]
(test bar) (plate)
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Thermo mechanical Properties – DMA Torsion Test
Increasing of glass transition temperature and remaining
stiffness by means of crosslinking.
TOR
SIO
NA
L M
OD
ULU
S G
` [N
/mm
²]
TEMPERATURE [°C]
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Fiber-Matrix bonding of PA6
Fiber pull out force increased with crosslinked material
=> Improved strength behaviour
Not crosslinked Crosslinked (99 KGy)
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Tribological Properties
MATERIAL: PA66 (dry)
WEA
R C
OEF
FIC
IEN
T [1
0-6m
m³/N
m]
FRIC
TIO
N F
AC
TOR
µ
IRRADIATION DOSE [KGy]Pin-Disc equipmentDisc: steal (Rz = 1,5 µm)T=100°C; v=0,5 m/s; p=4 N/mm²
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Tensile Test in accordance to DIN 2156; 2mm/Min; σmax
TEN
SILE
STR
ENG
TH [N
/mm
²]
INJECTION SEQUENCE1./2. Component
Irridiationwithout
Influence on Weld line strength
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Influence of molding
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Abrasion behaviour
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Surface pressure
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Surface roughness
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Influence of Temperature
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Sliding speed
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Abrasion behaviour in different layers
Not crosslinked
crosslinked
Qua
si-A
mor
ph
Sem
i-kris
talin
ear
ea
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Stress crack resistance
Not crosslinked Crosslinked (99 KGy)Crosslinked (33 KGy)
Crosslinked areas prevent disentanglement of molecules => higher stress crack resistance
INDICATOR A2 INDICATOR A1 INDICATOR A1
Bending test in accordance to DIN 4599R = 50mm, ε = 3,8%30% ZnCl224h test
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Long term behaviour
Not crosslinked crosslinked
TemperaturTime
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
PA 6.6 unreinforced
PA 6.6 25% glassfiber reinforced
PA 6.6 25% carbonfiber reinforced
PA 6.6 35% carbonfiber reinforced special lubricant
PBT 20% glassfiber reinforced
crosslinked
Not crosslinked
6,00E-06
7,11E-06
2,20E-062,00E-06
7,35E-06
2,00E-06
5,86E-06
1,97E-06
8,50E-07
6,17E-06
0,0E+00
1,0E-06
2,0E-06
3,0E-06
4,0E-06
5,0E-06
6,0E-06
7,0E-06
8,0E-06
Tribological properties / abrasion coefficient
crosslinked
Not crosslinked
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
PA66unverstärkt PA66 GF25
PA66 CF25PA66 CF35
L05 PBT GF20PA11
crosslinked
Not crosslinked
0,80
0,35
0,07
0,360,45
0,75
0,82
0,38
0,07
0,36 0,42
1,02
0
0,2
0,4
0,6
0,8
1
1,2
Tribological properties / frictional index
crosslinked
Not crosslinked
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
0
20
40
60
80
100
120
PA6unverstärkt
PA66 GF25 PA66 CF25 PA66 CF35L05
PBT GF20 PA11
Effects of crosslinking on the glass transition
crosslinked / dry
not crosslinked / dry
crosslinked / conditioned
not crosslinked / conditioned
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
Crosslinkable Materials from PTS:
PE, PP
TPE-E, TPU
PA11, PA12, PEBA
PBT
PA6, PA66
PA9T
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
.... mechanical properties- Increase of Module- Increase of mech. Strength (esp. Long term)- Reduction of Elongation at break- Reduction of creep behaviour- Increase of hardness- Increase of wear resistance- Increase of Tear strength- Increase of welding line strength - Increase of crack resistance- Improvement of Memory Effect
.... thermal properties- Increase of Heat deflection Temperature- Increase of Flame retardant
.... chemical properties- Gradual increase of resistance against chemicals- Reduction of solubility - Reduction of swelling behaviour
Increase of ....(Thermoplastic Materials)
Copyright, 2005 © PTS-Marketing GmbH, Tauberzell
END