DELO - Stefano Farina
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1 Pretreatments of plastics AIPI - Milano, 15 May 2014 DELO - Stefano Farina
2 Suitable and unsuitable materials compression shear strength [MPa] KB PB 4494 KB PB 4494 PUR 9694 compression shear strength [MPa] PUR polyamide cleaned polyamide + Primer 0 KB PB 4494 PB 4494 KB PUR 9694 PUR 9694 POM cleaned POM + Primer
3 Development of surface tension Influence of force at the interface Influence of force inside the liquid Definition of surface tension: Amount of energy that must be supplied to a liquid to create a new surface of 1 cm² 01/2013
4 Contact Angle: poor wetting Wetting angle α large Surface tension σ substrate < σ adhesive Adhesive work < cohesive work
5 Contact angel: good wetting Surface tension: Surface energy: Water 73 mnm -1 Adhesives 35 mnm -1 PTFE (Teflon) 19 mnm -1 PP 29 mnm -1 Wetting angle α small Surface tension σ substrate >σ adhesive Adhesive work > cohesive work mnm -1 [millinewton/m]
6 Contact Angle: basics Optimum to sufficient wetting: α < 30 Incomplete to missing wetting: 90 < α < 180 Surface tension: Adhesives 35 mnm -1 Water 73 mnm -1.
7 Suitable materials Surface energy of some typical plastics: Good for bonding PA (49 57 mn/m) PBT (35 38 mn/m) LCP (33 37 mn/m) PC (33 37 mn/m) ABS (35 42 mn/m) PVC (38 mn/m) PMMA (33 44 mn/m) Bad for bonding PE (31 mn/m) PP (29 mn/m) PTFE (19 mn/m) POM (36 mn/m)
8 Basics - Classification of methods Surface pretreatment preparation pretreatment after treatment cleaning mechanical acclimatization degreasingng physical chemical electro-chemical application of bonding agents application of primers (conservation)
9 Overview of popular methods grinding, etching physical primer** blasting methods* metals Most effective method: glass, ceramics plastics wood Alternative or complementing method: *) Physical methods: Corona, flaming, low-pressure plasma, atmospheric pressure plasma **) Primer attuned to adhesive
10 Primer Target: Considerable increase of the compound strength of adhesives difficult to bond DELO-primer for adhesives DELO-PRE 3003 adhesive agent for silicone adhesives DELO-PRE 2005 adhesive agent for cyanoacrylates DELO-SACO-SIL E adhesive agents for epoxy resins
11 Physical methods Corona Thermal pretreatment Low-pressure plasma Atmospheric pressure plasma Target: Chemical change by supplying kinetic, electrical and thermal energy
12 Corona-discharge High voltage discharge: U = kv f = khz Target: molecule fission and reaction with ozone, oxygen and nitric oxide Consequence: polar surfaces
13 Diagram: Compression shear strength DELO-DUOPOX AD895 - ABS/PA Blend Degreased Corona Druckscherfestigkeit (MPa) Initial value 2 w 85 C/ 85% humidity 2 w 40 C/ 100% humidity
14 Flaming Cracking on the surface New bonds with O 2 Polar surface
15 Diagram: Compression shear strength DELO-DUOPOX AD895 - PA 6.6 GF30 Degreased 25 Flaming Compression shear strength (MPa) Initial value 2 w 85 C/ 85% humidity 2 w 40 C/ 100% humidity
16 Low-pressure plasma Ar Ar + + e - O 2 2 O e -
17 Diagram: Compression shear strength 25 DELO-PUR PA 6.6 GF30 Degreased Corona Compression shear strength (MPa) Low-pressure plasma Flaming 0 Initial value 2 w 85 C/ 85% humidity 2 w 40 C/ 100% humidity
18 Atmospheric pressure plasma Voltage supply Gas supply (compressed air) Screen with boreholes Discharge area Insulator Electrode Stainless steel housing Plasma nozzle Plasma (with potential) Plasma (potential-free) Substrate
19 Diagram: Compression shear strength 30 DELO-DUOPOX AD895 - PBT/PET Blend GF20 Degreased Compression shear strength (MPa) Atmospheric plasma 0 Initial value 2 w 85 C/ 85% humidity 2 w 40 C/ 100% humidity
20 Diagram: Compression shear strength 30 DELO-DUOPOX AD895 - PBT/PET Blend GF20 Degreased 25 Corona Druckscherfestigkeit (MPa) Atmospheric pressure plasma Low-pressure plasma Flaming 5 0 Initial value 2 w 85 C/ 85% humidity 2 w 40 C/ 100% humidity
21 Overview Amorphous Amorphe plastics Kunststoffe Semi-crystalline Teilkristalline plastics Kunststoffe ABS Acrylnitril Butadien Styrol LCP flüssig-kristalline Polymere ASA Acrylnitril Styrol Acrylester PA 6 Polyamid 6 COC Cyclopolyolefinpolymere; Topas PA 6 GF Polyamid 6 gefüllt MBS Methylmethaccrylat-Butadien-Styrol Copolymer PA 6.6 Polyamid 6.6 PC Polycarvonat PBT Polybutylenterephtalat gefüllt 30% PC ABS Polycarbonat/ Acrylnitril Butadien Styrol PE Polyethylen PC ASA Polyphenylenether Acrylnitril Styrol Acrylester PEEK Polyetheretherketon PEC Chlorieres Polyehtylen PET Polyethylenterephtalat PECPSU Chlorieres Polyehtylen/ Polysulfon PFA Perfluoro-Alkoxyalkan PEI Polyetherimid POM Polyoxymethylen PES Polyethersulfon PP Polypropylen PMMA Polymethylmethacrylat PTFE Polytetraflourethylen PPE PA Polypenylenether Polyamid PVDF Polyvinylidenfluorid PPE SB Polyphenylenether Styrol Butadien PPO Polyethylenoxid PPSU Polyphenylensulfid PS Polystyrol PSU Polysulfon PVC Polyvinylchlorid SAN Styrolacrylnitril SB Styrol Butadien
22 PC no improvement with pretreatment Compression shear strength PC bonded verklebt with mit PB PB [MPa] gereinigt Corona A-Plasma ND-Plasma Beflammung 5 0 Anfangswert 85 /85% Test 40 /100% Test Curing 60 s 60mW/cm² LUX 03S
23 PC-ABS no improvement with pretreatment 30 Bayblend Bayblend T65 (PC-ABS) T65 bonded (PC-ABS) with verklebt MP AD0660 mit MP AD066 Compression Druckscherfestigkeit shear strength [MPa] [MPa] gereinigt Corona A-Plasma ND-Plasma Beflammung 0 Anfangswert 85 /85% Test 40 /100% Test Aushärtung 60 min 100 C incl. Aufheizzeit
24 PBT Pretreatment improves adhesion PBT Pocan PBT 3235 Pocan bonded 3235 with verklebt MP AD066 mit MP AD Compression Druckscherfestigkeit shear strength [MPa] gereinigt Corona A-Plasma ND-Plasma Beflammung 0 Anfangswert 85 /85% Test 40 /100% Test Curing 60 min. 100 C incl. heating time
25 PA 6.6 Pretreatment improves adhesion PA 6.6 PA Durethan 6.6 Durethan A30S H2.0 A30S bonded H2.0 with verklebt MP AD066 mit MP AD mv mv = Materialverformung 50 Compression Druckscherfestigkeit shear strength [MPa] gereinigt Corona A-Plasma ND-Plasma Beflammung 0 Anfangswert 85 /85% Test 40 /100% Test Curing 60 min. 100 C incl. heating time
26 Competence in the laboratory Testing of mechanical properties universal testing machines (500 N up to 100 kn); die-shear-tester (0 up to 5 kg) Climate storage Climate cycles (-20 C up to +100 C); constant climate (85 C, 85 % r. h.) Splash water test (40 C, 98 % rel. humidity) Thermal shock testing (-70 C up to +200 C) Temperature storage without change, at one temperature each (-30 C up to +250 C)
27 Competence in the laboratory Steam sterilization Pressure Cooker test (100 C, 1,1 bar, 100 % rel. LF) in the autoclave Determination of physical and chemical properties DSC, CS-rheometer, IR-spectroscopy, TMA-analysis, shore-hardness test, refractometer Surface pretreatment Low-pressure plasma, atmospheric pressure plasma, flaming, Corona, sand blasting Image processing and documentation Travelling microscope (resolution 0,1 µm)
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