Gradient Integrated Layered Coatings and Additives

J. Baghdachi1, and Gilbert Witte2 1Eastern Michigan University 2Paderborn university, Germany 1Innovative Technical Systems Corp. USA [email protected] and Coatings Industry-2019

Estimated worth of goods using polymers and Cost & Performance coatings $ 4-5 Trillion Inherently Multi-functionality Estimated Functional worth of Materials coatings and €/$ 5-9 $ 149 Billion Green Coatings Billion Sustainability

Global industry survey, April. 2019 (Americas, EU, JP/KR) Trends in Coating Technology Development-2019

Coatings Wish List (Opportunities)

. High performance coatings from sustainable materials……………….1 . Multi-functional coatings……………………………………………… 2 . Zero VOC waterborne coatings……………………………………… 3 . High-performance primerless/stratifying coatings…………………. 4 . Self-repair/easy-clean coatings……………………………………… 5 . Low-temperature curing coatings…………………………………… 6 . On-command cure/Instant set coatings*…………………………...... 7 . Corrosion and degradation sensing coatings……………………… 8 . Bioactive and Smart coatings……………………………………….. 9 . Super high solids automotive/industrial coatings………………….. 10 Global industry survey, April. 2019 (Americas, EU, JP/KR) Materials for Coatings-2019

Unmet Global Material Needs (Opportunities)

. Bisphenol-A and hybrid polymers……………………………………… 1 . Property switching polymers 2 . Reactive coalescent agents……………………………………………. 3 . Multifunctional polymers* 4 . Responsive and switchable additives…………………………………. 5 . free, non-whitening emulations 6 . Drop-in pigments………………………………………………………… 7 . Phase-changing waterborne 8 . Low-temperature curing powder coating resins*…………………….. 9 . Superhydrophobic and antimicrobial polymers** 10

Global industry survey; April 2019 (America, EU, JP/KR) * Available ** Custom made Formulation Succss Rate Survey*

Industry and technology survey (2016-2018-USA) Ave. 12 formulation attempts per formula 46%** of coating formulation attempts fail initial laboratory testing 52 reformulation attempts 61%** of samples failed accelerated exposure evaluations during a 10-year period

57%** of coating samples marginally meet set specifications

6%** of samples exceed set specification Failed formulations were reformulated and retested

* (N. America, EU, S. America, JP/Korea) Successful formulations were **Rounded and normalized Standard deviation +/- 3 scaled up Rational Coating Formulation - Concepts and Applications

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 Reliability-based Methodology Science vs vs Durability-based Methodology Chemistry

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

Interactions of liquid ingredients lower the entropy *

ΔGm = ΔHm - TΔSm

Interaction Forces in liquid Coatings Surfactant HOROR

. London dispersion CaCO3 . Dipole-dipole Rheology . Hydrogen bonding Acid modifier . Ion-dipole catalyst . Ion-ion *Measured using Calorimeter DS = q/T Rational Coating Formulation-Concept and Applications-

Material functions and interactions

• additives interactions • Coalescent agent interactions • Diluents vs • Dispersion agent deficiency • 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

Example Automotive acrylic waterborne basecoat resin interactions

100 mg/KOH* 135 mg/KOH*

RCA demand RCA demand Combined material interactions Flow agent Flow agent produce out of phase domains of Azeotrope mix Azeotrope mix agglomerated materials that hinder Color stability Color stability intended function of ingredients. Clearcoat Adhesion Clearcoat adhesion Homogeneity Homogeneity Viscosity Viscosity Hot box stability Hot box stability 1000 hr. QUV** 1000 hr. QUV** Strike in resistance Strike in resistance Non-uniform coating film and random material distribution * Same MW; ** 2K PU clearcoat @ 40 µ DFT Industrial baking enamel

Thermosetting acrylic resin 28.50 Methyl ethyl ketone 6.444 Thermosetting acrylic resin 27.250 Xylenes 2.123 1988 2018 Methyl ethyl ketone 6.200 Polyester reactive diluent K-flex 181 2.000 formula formula Xylenes 2.123 BYK 333 anti-crater 0.024 Polyester reactive diluent K-flex 181 2.000 Methyl amyl ketone 1.740 Cypar 9 2.951 Calcium naphthenate 0.249 Catalyst Nacure 3525 0.513 Cypar 9 1.001 Melamine Cymel 1156 12.00 Catalyst Nacure 3525 0.513 Red iron oxide 8.001 Catalyst Nacure 2500 0.135 21% less VOC Kaolin clay Optiwhite 29.45 Melamine Cymel 1156 12.77 Tinuvin 123 0.225 Microgel NAD resin 3.262 14 Ingredients Barium sulfate 3.900 Red iron oxide 8.001 17% less costly Yellow horizontal mill 0.450 Kaolin clay Optiwhite 24.56 Sodium Bentonite 2.000 Tinuvin 123 0.225 Methanol 1.960 Tinuvin 384B 0.701 Lower cost silane PC 3100 0.543 Lower VOC 14 ingredients Baryte (Barium sulfate) 1.900 More efficient Yellow horizontal mill 0.450 Sodium Bentonite 2.434 Same performance Methanol 2.667

21 ingredients 14 ingredients White mildew/mold resistant exterior wall paint

Ingredients Amount Kg 19.06 Calgon N neu 0.06 Borchi Gen NA 40 0.39 Borchi Gen DFN 0.29 C36H70O19 Natrosol 330 Plus 0.22 Hydroxyethyl cellulose Diuron AMP90 0.11 Kronos 2300 22.04 Mikro Talk IT extra 2.76 Thickener agent and Diuron Durcal 5 16.53 interactions Dowanol DPnB 0.39 Diuron 80 0.3 Borchi Gel 0434 0.43 Acronal 290D 36.87 Byk 032 0.34 Oxylink 3102 0.30 Ineffective incompatible Diuron Gradient Integrated Layer Functionality

Why integrated layer technology

. Functionality and Efficiency >95% of . . Adhesion Cost and Economy . Appearance coatings Bioactivity . Bioactivity/fouling are . Corrosion surface Coating . Gloss substrate . Hydrophobicity… Active and Adhesion . Reflectivity Multifunctional . Scratch resistance Corrosion . Texture … . … Integrated Layered Materials (stratification)

. Most synthetic materials possess a defined surface and behave statically

. Most natural materials possess multi-functional and integrated surface layers

Most coating applications require primer, or intermediate coatings Certain chemical agents have specific function and location

***

Iron surface : Fe2(CO3)3, Fe(OH)3… … Surface Functionality-Gradient Integrated Layer

Multi-layered Coatings Polymer Stratification Phenomenon

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

Funke, W., J. Oil Colour Chem. Assoc., 59 (1976) 398-403 Rational Formulation Concept/Applications

2% Adhesion Promoter 7% Corrosion Inhibitor Scratch, slip, antimicrobial, gloss, 50 µ flow, anti crater, etc. agents

Air 10 µ Corrosion inhibitor, Substrate Adhesion promoters etc. ~0.11 Adhesion Promoter ~1.2 Corrosion Inhibitor

0.21% 1% Zinc Phosphate APTMSilane 0.35% 0.12%

0.11% CRS

SEM/EDX Analysis Integrated Layered Materials

Area 2 = 1.574% Area 1 Area 2

Area 1 = 9.787%

Elt. Line Intensity Error Atomic Conc Units Elt. Line Intensity Error Atomic Conc Units (c/s) 2-sig Ratio (c/s) 2-sig Ratio

C Ka 92.61 2.722 11.7892 85.211 wt.% C Ka 22.69 1.347 9.0377 74.729 wt.%

O Ka 2.56 0.453 1.0000 11.015 wt.% O Ka 3.36 0.518 1.0000 9.628 wt.% F Ka 0.31 0.158 0.0464 0.607 wt.% F Ka 1.04 0.288 0.1108 1.267 wt.% Si Ka 48.64 1.973 0.5062 9.787 wt.% Si Ka 20.85 1.292 0.1523 1.574 wt.% Cl Ka 15.97 1.130 0.1582 3.862 wt.% Cl Ka 9.46 0.870 0.0618 2.320 wt.% 100.000 wt.% 100.000 wt.% Integrated Layered Materials

Liquid Adhesion promoter High surface area 5-10 µ particles Silane(s), Carboxylic Acids RT, physical+ treatment DI Rinse Neutral agents Physical treatment

Stratifying Adhesion Filter/dry Powder Adhesion promoter Promoter Shelf-life, 6 Mo. @40% RH/30 oC

Liquid Adhesion promoter Crown Ether +Aprotic Stratifying Promoter Silane(s), Carboxylic Acids Shelf-life, 12 Mo. Neutral agents Physical treatment @40% RH/25 oC

Stratification Rate 75-95% SEM/EDX Analysis Integrated Layered Materials : Corrosion Inhibitor

2K Amidoamine-cured Epoxy primer/CRS

- Δ, H2O, OH Ce+3 Ce+3

o ΔEnviron > Tm =40 C

550 hrs 810 hr ASTM B117 Gradient Integrated Layered Coatings

Controlled Hetero-phase Formation ΔGm = ΔHm - TΔSm

Incompatible low surface energy polymer Incompatible high surface energy polymer kinetically competing reactions

Stratified film Stages of Stratification

Solvent/Water

Phase separation vs time/temp/crosslinking Composition and Reaction Kinetics

One component multi resin solvent borne OCH CF CF OCH2CF2CF3 2 2 3 CH CH composition CH2 3 2 Acrylic polyol OH H2CCCH2O CH2CCH2 O CH2 CCH2 OH o CH x CH y Shelf-life > 90 days at 25 C 50% RH 3 3 3CH + OH Value 125 Composition/Solvent B

Composition/Solvent A HMMM-MF or Isocyanurate of IPDI Epoxy Curing Agent: Lewis Acid Complex Or Aromatic Amidoamine Driving forces 120-140 oC Preferential reactivity Surface energy Differential And more….

75-105 oC M/F; PU –Acrylic/Fluoropolymer Epoxy/silicone primer Composition and Reaction Kinetics

Area 1

Elt. Intensi Error Atomic Conc Units ty 2-sig Ratio (c/s) C 4.38 0.592 73.458 20.331 61.480 wt.% 0 O 0.59 0.218 3.613 1.0000 3.701 wt.%

Area 1 EDX F 4.58 0.605 10.183 2.8183 12.384 wt.% Bake schedule Si 10.34 0.909 3.009 0.8327 0.409 wt.% Staged bake: S 1.14 0.302 0.335 0.0929 0.689 wt.% o Cl 31.89 1.597 9.402 2.6022 21.338 wt.% 30 Min @ 75-110 C 100.00 100.00 wt.% 30 Min @ 110-140 oC 0 0 Composition and Reaction Kinetics

Area 2

Elt. Intensit Error Atomic Atomic Conc Units y 2-sig % Ratio (c/s) C 1.87 0.387 71.945 10.891 55.005 wt.% 0 O 0.49 0.197 6.606 1.0000 6.728 wt.% Area 2 EDX 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.% 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 Composition and Reaction Kinetics

Et3Al2Cl3

LF-200+ HDI+ Dendrimer Topcoat

Intermediate coat Kinetic and Mass Transfer Control Characterization and Instrumental Analysis

Adhesion 5B, MEK rubs > 200

F, 10.851 Si, 0.741 SEM image and EDX of

stratified coating

F, 0.00 Atomic concentration of selected Si, 15.760 elements in stratified coating Composition and Stratification

SEM of TiO2 pigmented system

Area1 Elt. Line Intensity Error Atomic Atomic Conc Units K-Ratio (c/s) 2-sig % 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 EDX elemental analysis of 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 TiO2 = 0.354 area 1 and 2 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 Error Atomic Atomic Conc Units K-Ratio (c/s) 2-sig % Ratio TiO2 = 23.60 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

Key Points

 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

Challenging and Shattering Conventions Thank You!

Jamil Baghdachi [email protected]