J. Baghdachi1, and Gilbert Witte2

1Eastern Michigan University2Paderborn university, Germany

1Innovative Technical Systems Corp. USAjbaghdach@emich.edu

Gradient Integrated Layered Coatings and Additives

Polymers and Coatings Industry-2019

Estimated

worth of goods

using

polymers and

coatings

4-5

TrillionEstimated

worth of

coatings and

149

Billion

$

$

Multi-functionality

Green Coatings Sustainability

Inherently FunctionalMaterials

€/$ 5-9Billion

Cost & Performance

Global industry survey, April. 2019 (Americas, EU, JP/KR)

Trends in Coating Technology Development-2019

High performance coatings from sustainable materials………………. Multi-functional coatings……………………………………………… Zero VOC waterborne coatings……………………………………… High-performance primerless/stratifying coatings…………………. Self-repair/easy-clean coatings……………………………………… Low-temperature curing coatings…………………………………… On-command cure/Instant set coatings*…………………………........ Corrosion and degradation sensing coatings……………………… Bioactive and Smart coatings……………………………………….. Super high solids automotive/industrial coatings…………………..Global industry survey, April. 2019 (Americas, EU, JP/KR)

12 3 4 5 6 7 8 9 10

Coatings Wish List (Opportunities)

Bisphenol-A and hybrid polymers……………………………………… Property switching polymers Reactive coalescent agents……………………………………………. Multifunctional polymers* Responsive and switchable additives…………………………………. Surfactant free, non-whitening emulations Drop-in pigments………………………………………………………… Phase-changing waterborne resins Low-temperature curing powder coating resins*…………………….. Superhydrophobic and antimicrobial polymers**

12 3 4 5 6 7 8 9 10

Unmet Global Material Needs (Opportunities)

Global industry survey; April 2019 (America, EU, JP/KR)

Materials for Coatings-2019

* Available ** Custom made

Formulation Succss Rate Survey*

Industry and technology survey (2016-2018-USA)

46%** of coating formulation attempts fail initial laboratory testing

61%** of samples failed accelerated exposure evaluations

57%** of coating samples marginally meet set specifications

6%** of samples exceed set specification

Ave. 12 formulation attempts per formula

52 reformulation attempts during a 10-year period

* (N. America, EU, S. America, JP/Korea) **Rounded and normalized Standard deviation +/- 3

Failed formulations were reformulated and retested

Successful formulations were scaled up

Rational Coating Formulation differs from conventional approaches in that it assesses potential interactions among ingredients prior to formulation.

The approach is similar to material reliability assessment practiced by aeronautic, photonic, weaponry and electronic industries to develop reliable and high-performance products

Material Science

vs Chemistry

What makes coatings complex are not the obvious reactions but, interactions among coating ingredients

Reliability-based Methodologyvs

Durability-based Methodology

Rational Coating Formulation - Concepts and Applications

Rational Formulation ConceptInteractions of liquid ingredients lower the entropy *

ΔGm = ΔHm - TΔSm

Interaction Forces inliquid Coatings

London dispersion Dipole-dipole Hydrogen bonding Ion-dipole Ion-ion

Acid catalyst

Rheology modifier

Surfactant HOROR

CaCO3

*Measured using CalorimeterDS = q/T

Rational Coating Formulation-Concept and Applications-

Material functions and interactions

• Resin additives interactions• Coalescent agent interactions• Diluents vs solvents• Dispersion agent deficiency• Polymer and functionality imbalance• Rheology control agent interactions• Adhesion promoter distribution• Corrosion inhibitor distribution• …

Any existing coating can be improved for performance and cost!

Rational Coating Formulation - Concepts and Applications

ExampleAutomotive acrylic waterborne basecoat resin interactions

100 mg/KOH*

RCA demandFlow agentAzeotrope mixColor stabilityClearcoat AdhesionHomogeneityViscosity Hot box stability1000 hr. QUV**Strike in resistance

135 mg/KOH*

RCA demandFlow agentAzeotrope mix Color stabilityClearcoat adhesionHomogeneityViscosityHot box stability1000 hr. QUV**Strike in resistance

* Same MW; ** 2K PU clearcoat @ 40 µ DFT

Combined material interactions produce out of phase domains of

agglomerated materials that hinder intended function of ingredients.

Non-uniform coating film and random material distribution

Industrial baking enamel

Thermosetting acrylic resin 28.50

Methyl ethyl ketone 6.444

Xylenes 2.123

Polyester reactive diluent K-flex 181 2.000

BYK 333 anti-crater 0.024

Methyl amyl ketone 1.740

Calcium naphthenate 0.249

Cypar 9 1.001

Catalyst Nacure 3525 0.513

Catalyst Nacure 2500 0.135

Melamine Cymel 1156 12.77

Microgel NAD resin 3.262

Red iron oxide 8.001

Kaolin clay Optiwhite 24.56

Tinuvin 123 0.225

Tinuvin 384B 0.701

Epoxy silane PC 3100 0.543

Baryte (Barium sulfate) 1.900

Yellow horizontal mill 0.450

Sodium Bentonite 2.434

Methanol 2.667

21 ingredients

Thermosetting acrylic resin 27.250

Methyl ethyl ketone 6.200

Xylenes 2.123

Polyester reactive diluent K-flex 181 2.000

Cypar 9 2.951

Catalyst Nacure 3525 0.513

Melamine Cymel 1156 12.00

Red iron oxide 8.001

Kaolin clay Optiwhite 29.45

Tinuvin 123 0.225

Barium sulfate 3.900

Yellow horizontal mill 0.450

Sodium Bentonite 2.000

Methanol 1.960

14 ingredients

1988formula

2018formula

Lower costLower VOC

More efficientSame performance

21% less VOC14 Ingredients17% less costly

14 ingredients

White mildew/mold resistant exterior wall paint

Ingredients Amount KgWater 19.06Calgon N neu 0.06 Borchi Gen NA 40 0.39 Borchi Gen DFN 0.29 Natrosol 330 Plus 0.22 AMP90 0.11 Kronos 2300 22.04 Mikro Talk IT extra 2.76 Durcal 5 16.53 Dowanol DPnB 0.39 Diuron 80 0.3Borchi Gel 0434 0.43 Acronal 290D 36.87 Byk 032 0.34 Oxylink 3102 0.30

Diuron

Ineffective incompatible Diuron

C36H70O19Hydroxyethyl cellulose

Thickener agent and Diuron interactions

Why integrated layer technology

Functionality and Efficiency Cost and Economy

Gradient Integrated Layer Functionality

>95% of coatings

are surface

Active and Multifunctional

Adhesion Appearance Bioactivity/fouling Corrosion Gloss Hydrophobicity… Reflectivity Scratch resistance Texture …

AdhesionCorrosion…

Bioactivity

substrateCoating

Integrated Layered Materials (stratification)

Most synthetic materials possess a defined surface and behave statically

Most natural materials possess multi-functional and integrated surface layers

Iron surface : Fe2(CO3)3, Fe(OH)3… …

***

Most coating applications require primer, or intermediate coatings

Certain chemical agents have specific function and location

Multi-layered Coatings

Surface Functionality-Gradient Integrated Layer

Polymer Stratification Phenomenon

Funke, W., J. Oil Colour Chem. Assoc., 59 (1976) 398-403

ATIR and SEM/EDX of functional polymers show different functional groups and elemental conc. on the surface vs bulk

Applications Surface activity* Sensory functions* Economy of process Sustainability

Rational Formulation Concept/Applications

50 µ

2% Adhesion Promoter 7% Corrosion Inhibitor

Substrate

10 µ

~0.11 Adhesion Promoter ~1.2 Corrosion Inhibitor

Scratch, slip, antimicrobial, gloss, flow, anti crater, etc. agents

Corrosion inhibitor,Adhesion promotersetc.

Air

Zinc Phosphate0.12%

1%

CRS

APTMSilane

0.11%

0.35%

0.21%

SEM/EDX Analysis

Integrated Layered Materials

Elt. Line Intensity(c/s)

Error2-sig

AtomicRatio

Conc Units

C Ka 22.69 1.347 9.0377 74.729 wt.%

O Ka 2.56 0.453 1.0000 11.015 wt.%

F Ka 0.31 0.158 0.0464 0.607 wt.%

Si Ka 48.64 1.973 0.5062 9.787 wt.%

Cl Ka 15.97 1.130 0.1582 3.862 wt.%

100.000 wt.%

Elt. Line Intensity(c/s)

Error2-sig

AtomicRatio

Conc Units

C Ka 92.61 2.722 11.7892 85.211 wt.%

O Ka 3.36 0.518 1.0000 9.628 wt.%

F Ka 1.04 0.288 0.1108 1.267 wt.%

Si Ka 20.85 1.292 0.1523 1.574 wt.%

Cl Ka 9.46 0.870 0.0618 2.320 wt.%

100.000 wt.%

Area 1

Area 1 = 9.787%

Area 2

Area 2 = 1.574%

Integrated Layered Materials

RT, physical treatment DI RinseHigh surface area 5-10 µ particles

+Physical treatment

Liquid Adhesion promoterSilane(s), Carboxylic Acids

Neutral agents

Filter/dry Powder Adhesion promoterStratifying Adhesion

PromoterShelf-life, 6 Mo.

@40% RH/30 oC

Crown Ether +Aprotic Solvent

Physical treatment

Liquid Adhesion promoterSilane(s), Carboxylic Acids

Neutral agents

Stratifying PromoterShelf-life, 12 Mo. @40% RH/25 oC

Stratification Rate 75-95% SEM/EDX Analysis

: Corrosion Inhibitor

550 hrs 810 hrASTM B117

2K Amidoamine-cured Epoxy primer/CRS

Ce+3Ce+3Δ, H2O, OH-

ΔEnviron > Tm =40 oC

Integrated Layered Materials

Gradient Integrated Layered Coatings

Incompatible low surface energy polymerIncompatible high surface energy polymerkinetically competing reactions

ΔGm = ΔHm - TΔSmControlled Hetero-phase Formation

Stratified film

Stages of Stratification

Phase separation vs time/temp/crosslinking

Solvent/Water

Composition and Reaction Kinetics

CH2CCH3

CH3

CH2

OCH2CF2CF3

OH H2CCCH2

CH3

CH2O

OCH2CF2CF3

OHCCH2

CH2

CH3

CH2O yx

Epoxy Curing Agent: Lewis Acid ComplexOr Aromatic Amidoamine

HMMM-MF or Isocyanurate of IPDI Composition/Solvent A

Composition/Solvent B

120-140 oC

75-105 oC

Driving forces

Preferential reactivitySurface energy DifferentialAnd more….

One component multi resin solvent bornecompositionShelf-life > 90 days at 25 oC 50% RH

Epoxy/silicone primer

M/F; PU –Acrylic/Fluoropolymer

Acrylic polyolOH Value 125+

Composition and Reaction Kinetics

Elt. Intensity(c/s)

Error2-sig

AtomicRatio

Conc Units

C 4.38 0.592 73.458 20.3310

61.480 wt.%

O 0.59 0.218 3.613 1.0000 3.701 wt.%

F 4.58 0.605 10.183 2.8183 12.384 wt.%

Si 10.34 0.909 3.009 0.8327 0.409 wt.%

S 1.14 0.302 0.335 0.0929 0.689 wt.%

Cl 31.89 1.597 9.402 2.6022 21.338 wt.%

100.000

100.000

wt.%

Area 1

Area 1 EDXBake schedule

Staged bake:30 Min @ 75-110 oC30 Min @ 110-140 oC

Composition and Reaction Kinetics

Elt. Intensity(c/s)

Error2-sig

Atomic%

AtomicRatio

Conc Units

C 1.87 0.387 71.945 10.8910

55.005 wt.%

O 0.49 0.197 6.606 1.0000 6.728 wt.%

F 0.09 0.086 0.456 0.0691 0.552 wt.%

Si 49.71 1.994 20.462 3.0975 26.581 wt.%

S 0.53 0.207 0.294 0.0445 0.600 wt.%

Cl 0.49 0.198 0.237 0.0359 15.35 wt.%

100.000 100.000 wt.%

Area 2

Area 2 EDX

Composition and Reaction Kinetics

Physical properties Test results

Inter-coat adhesion/CRS adhesion 5B

Pencil hardness 1-2H

Impact resistance Forward 160, Reverse 80 lb.-Inch

MEK Rub (135/30 min or 140/30 min 75; 120

QUV Exposure 1450 hrs. In Progress

Corrosion resistance ASTM B117 940 hrs. In Progress

LF-200+ HDI+ Dendrimer

Kinetic and Mass Transfer Control

Et3Al2Cl3

Composition and Reaction Kinetics

Topcoat

Intermediate coat

Characterization and Instrumental Analysis

SEM image and EDX of stratified coating

Adhesion 5B, MEK rubs > 200

F, 10.851Si, 0.741

F, 0.00Si, 15.760

Atomic concentration of selected

elements in stratified coating

Composition and Stratification

Area1 Elt. Line Intensity

(c/s) Error 2-sig

Atomic %

Atomic Ratio

Conc Units K-Ratio

C Ka 8.52 0.825 86.573 180.7425 70.375 wt.% 0.2280 O Ka 0.11 0.094 0.479 1.0000 0.519 wt.% 0.0018 F Ka 0.72 0.241 0.956 1.9959 1.229 wt.% 0.0079 Si Ka 16.99 1.166 1.981 4.1359 3.766 wt.% 0.1013 Cl Ka 87.71 2.649 9.901 20.6715 23.758 wt.% 0.6522 Ti Ka 0.84 0.260 0.109 0.2279 0.354 wt.% 0.0088 100.000 100.000 wt.% Total

Area2 Elt. Line Intensity

(c/s) Error 2-sig

Atomic %

Atomic Ratio

Conc Units K-Ratio

C Ka 4.79 0.619 65.459 255.5590 39.990 wt.% 0.0939 O Ka 0.04 0.055 0.256 1.0000 0.208 wt.% 0.0005 F Ka 0.17 0.116 0.393 1.5331 0.379 wt.% 0.0014 Si Ka 101.46 2.849 20.860 81.4381 29.799 wt.% 0.4571 Cl Ka 15.28 1.106 3.337 13.0278 6.017 wt.% 0.0864 Ti Ka 44.79 1.893 9.695 37.8511 23.605 wt.% 0.3606 100.000 100.000 wt.% Total

SEM of TiO2 pigmentedsystem

TiO2 = 0.354

TiO2 = 23.60

EDX elemental analysis of area 1 and 2

Gradient Integrated layer technology maybe used to formulate and produce highly functional and reliable products and enhance efficiency of materials

Self-stratifying coatings can be regarded as sustainable process that reduces emissions, energy, and increases the cost and economy of coating formulation and application.

Rational Formulation concepts and applications will provide higher performance, novel, high efficiency and reliable coatings

Key Points

Challenging and Shattering Conventions

Thank You!

jbaghdachi@emich.eduJamil Baghdachi