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Chemical Analysis and Databases in the Paint Industry
Rich SimonGlobal Analytical NetworkJuly 19th, 2016
• Overview of Valspar and Analytical/Materials Science• Paint Analysis in the Industry• Example Analysis—Pyrolysis GC/MS of Latex Paint• New Databases• Color Databases• Questions and Contact Information
Agenda
Valspar Coatings
Objectives: Clarify working mechanisms of coatings’ performance that provides:
Design guidelines for continuous product improvements,
Better performance protocols, and
Root cause solutions of issues.
Materials Science/Analytical
4
Analytical Science
•Chemical problem solving/defect analysis
•Molecular analysis•Migration and
regulatory testing•Weathering
Physical Sciences
•New product development
•Method development•Customer line trials
MaterialsScience
ResearchGroup
4Valspar Business Confidential
• We do the same tests but for different reasons.• Therefore databases are built for different goals.
Paint Analysis in the Industry
Sample AnalysisGC/MSFT-IRSEM
XRF/ICPEtc. Goal
Determine Functionality,
Mechanism, and Impact on
Performance
GoalMatch
Ingredients, Formulas, etc.
for ComparisonsForensic
Industry
Mechanisms of Interaction
• Ultimately our goal is to get here!• Determining mechanisms which impact performance• Need to ID materials before you can do this.
Rheology Data
Paint Analysis Overview
Paint Sample
Solvents
Solvent Based
GS-MS orGC-FID
Waterborne
GS-MS or GC-FID
Resins
Solvent Based
FTIR
Pyrolysis(PY-GC-MS)
Saponification(SAP)
GPC
DSC (Tg)
Raman Spectroscopy
LC/MS
Waterborne
FTIR
Pyrolysis(PY-GC-MS)
GPC
DSC (Tg)
Raman Spectroscopy
LC/MS
Pigments
Ash
XRF (ICP) FTIR
Raman Spectroscopy
Additives
Solvent Based
Dries (Alkyd)
UV/HALS (HPLC/GC)
Waterborne
Surfactant (LC-MS)
Biocides (HPLC)
Rheology Modifiers
Physical
NVM %
Ash %
NVM %
P/B Ratio
Density (Wt/Gal)
We use databases in most of these areas!Areas are further subdivided from raw material for more details(i.e. resin monomers, surfactant/rheology modifier end groups, etc.)
• Numerous types of databases are used:– Some commercially available
• Coatings Technology Library—FSCT* (FT-IR)• NIST GC/MSD Library
– Many custom developed in-house– Also use color databases
• Focus on functionality and not formulations (i.e. paints)– Reverse Engineering/Competitive
• Cost Information• IP/Patent infringement
– Problem Solving/Customer/Internal R&D• General Technology• Failure mechanisms for coatings
– Regulatory• VOC• Packaging Oligomers
Databases at Valspar
*Federation of Societies for Coatings Technology
Competitive Latex Paint Analysis
• 4 Different Competitive Latex Paints Analyzed• What is Valspar interested in?
– Cost– Performance– IP protection Acrylic Monomers
Additives and larger fragments
Pyrolysis GC/MS
• Same Acrylic Monomers in the same ratio• Paint manufacturers use commodity acrylics
Latex Paint Analysis
• Database used for the following:• Acrylic Monomer ID (EI MSD)• Latex type
• Based on ratio of monomers
• Link back to manufacturers
• ~300 Latex types in database
• Additives area shows bigger differences• Databases used for identification of additive fragments (EI MS)
Latex Paint Analysis
o Urethanea. Indicates presence of HEUR*b. Added for flow and application
performancec. Lack of HEUR means HASE** or
Cellulosic most likely present
o Butyl Citratea. Coalescing agentb. Helps polymer diffusion
*Hydrophobically Modified Ethylene Oxide Urethane Rheology Modifier (HEUR)**Hydrophobically Modified Alkali Swellable Emulsions (HASE)
• LC/MS/MS (RT, Mass, Fragmentation)– Surfactants– Organic Pigments/Colorants– Additives– Oligomers– Packaging Regulatory (<1000 daltons)
• Raman– Organic Pigments– Additives
• Solubility Parameters– Compatibility of materials
• Continuous updates to existing
New Databases
LC/MS/MS
Confocal Raman Microscope
Surfactant Analysis by LC/MS/MS:Identification of Nonylphenol Ethoxylate
13
6x10
0
0.1
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2.4
2.5
+ESI Scan (0.089-0.272 min, 12 scans) Frag=135.0V Igepal_CO-630.d
* 634.4510 2* 546.3880 1
* 722.5002 1
* 502.3562 1
* 810.5383 1
* 854.5569 1
* 458.3284 1 * 898.5763 1
942.5983 1
414.3037 1 986.6218 1
1030.6457 1
1074.6694370.2787
Counts vs. Mass-to-Charge (m/z)
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850 900 950 1000 1050 1100 1150 1200 1250 1300 1350 1400 1450
n = 4
n = 5
n = 6
n = 7
44 Da mass shift indicative of ethoxylation
Total Ion Mass Spectrum – Positive Ion Mode
Observed as ammonium ions
NH4+
OO
Hn
+ 44 Da
+ 44 Da
+ 44 Da
14
5x10
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2
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3
+ESI Product Ion (0.134 min) Frag=125.0V [email protected] (634.4500[z=1] -> **) Igepal_CO-630_MS2.d
89.0595
71.0857
57.0703 133.0847 247.2030
291.2288
165.0886
Counts vs. Mass-to-Charge (m/z)
20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680
OO
Nonylphenol terminal fragment ions
HOO
OOHO
OPEG terminal fragment ions
Tandem Mass Spectrum – Fragmentation of Nonylphenol Ethoxylate, n = 9
Chemical Formula: C6H13O3+
Exact Mass: 133.0859
Chemical Formula: C4H9O2+
Exact Mass: 89.0597
Chemical Formula: C17H27O+
Exact Mass: 247.2056
Chemical Formula: C19H31O2+
Exact Mass: 291.2319
Surfactant Analysis by LC/MS/MS:Identification of Nonylphenol Ethoxylate
End group and ethoxylation chain size help understand interactions
• Color Databases are used for color matching (refinish)– Spectrophotometer (Visible Spectrum between 400 – 700 nm)– Multi-angle stored. ~15k Colors in database. Also stored as CIELAB.– Coarseness for effect pigments– Also gather make, model, year, part of car taken, etc.
• Variation can be significant and needs to be known– Different OEM manufacturers/Different chemistry/technology– Variations in raw materials– Age/environmental conditions of the vehicle
Color Databases
