SCIENTIFIC SERVICES S/D INC October 2004 ASTM D 3556 RESEARCH Deposition on Glassware During Mechanical Dishwashing Background1 Preliminary Soil Exp Soils,2Levels, ½ Factorial 6-12 Precision of Evaluation Preparation of Standards20-24

BACKGROUND

PRELIMINARY EXPERIMENT - SENSITIVITY TO CURRENT D 3556 SOILS

Preliminary Test of Soil Effect - 2 Level Factorial Design – Main Effects Only Liquid and Powder commercial Detergents at recommended use level Equal Amounts of Tallow/Lard/Margarine Greasy Soil – 16 or 48g Oatmeal+Dry Milk ASTM Soil - 16g or 48g 165 ppm in Maytag MDB3700AWX

Conclusions from Preliminary Experiment All three variables have significant effects. Liquid and powder detergents react differently to soil kind and amount. Liquid Detergent gave more more spots than powder. Powder gave more film. Higher amounts of grease reduced film but had no effect on spots. Higher amounts of oatmeal reduced both film and spots. Additional work was done with more realistic levels of soils and the three soils – fat, starch and protein were each investigated.

INVESTIGATION OF EFFECTS OF THREE “SURFACE ACTIVE” SOILS Variables Liquid and Powder Commercial Detergents at Recommended Dosage Hi and Low Levels of Grease Dry Milk Oatmeal Levels chosen to approximate household amounts Maytag Model No. MDB3700AWX inexpensive model 165 ppm 2/1 Ca/Mg synthetic hard water Evaluate after 1,2 3 Cycles by Rating and by Ranking

Experimental Design – Half Factorial – 4 Variables – 2 levels RowsPatternDetergentGreaseOatmealDry MilkSpots & Film Response 1----Liquid4g16g4g 2--++Liquid4g30g16g 3-+-+Liquid16g 4-++-Liquid16g30g4g 5+--+Powder4g16g 6+-+-Powder4g30g4g 7++--Powder16g 4g 8++++Powder16g30g16g

Fractional Factorial Structure Factor Confounding Rules Dry Milk = Detergent X Grease X Oatmeal Aliasing Structure Detergent Grease Oatmeal Dry Milk Detergent X Grease = Oatmeal X Dry Milk Detergent X Oatmeal = Grease X Dry Milk Detergent X Dry Milk = Grease X Oatmeal

3rd Cycle Main Effects of 4 Variables from Experimental Design Evaluation by Ranking and by Rating against Standards

1 st, 2 nd & 3 rd Cycle Main Effects from 4 variable Experimental Design

Interactions from 4 Variable Design - Data from Evaluation by Ranking

Conclusions from study of three separate soils with Liquid and Powder Detergents Ranking results used. Ranking vs Rating Discussed Later At the lower levels of soil significant effects were still seen and interactions between the variables were important. Also, there were differences after 1, 2, and 3 cycles. Evaluation of 3 rd cycle glasses only show more grease gave more spots. More oatmeal caused more film. More dry milk gave less film. With Liquid Detergent there were more spots and Powder resulted in more film Including evaluations from all three cycles gives similar, but not identical, results. Grease causes both film and spots to increase. Oatmeal gives fewer spots. Dry Milk still gave less film. Powder detergent is preferred for less spotting but Liquid Detergent is better for less film.  There are many significant two way interactions between the variables. But, there is confounding because of the half-factorial experimental design, so don’t know whether the effects shown are soil-to-soil synergisms of their soil-detergent counterparts. The importance is that soil type and amount affect Detergent Performance differently and need to be taken into account.

Precision of Evaluation Comparison of evaluation of sets of glasses by ranking best to worst versus rating against ASTM Standards. Three Operators Three separated Sessions Analysis by JMP Statistical Software

Evaluation by Ranking and against Standards by 3 Observers 3 Times 24 Miscellaneous FL Glasses

Evaluation of Glasses by 3 Observers 3 Times – 24 FL Glasses - Statistics

Effect of 3 Operators and 3 Sessions on Evaluation of 24 Glasses from Experimental Design

Statistics by Ranking and vs Stds. for 2 Level 4 Variable Partial Factorial Experimental Design

Interactions Data from 4 Variable Design by Evaluation Against Standards

Interactions – 3 rd Cycle Results from 4 Variable Design Vs Standards and by Ranking

Conclusions about Rating vs Ranking Operator differences cause less error when relative performance is evaluated by a procedure to rank an experimental set of glasses than when assignment of ratings against standard glasses is used. Either procedure will allow for the measurement of significant differences in performance. And the operator error introduced by ranking is of low or significance. Ranking is less stressful than Rating. New data show that elapsed time before evaluation can be a factor and should be controlled.

Preparation of Spot and Film Standard Glasses After much effort to select glasses from actual laboratory runs as spot and film standards, we developed methods for making spotted and filmed glasses “synthetically. Spots were made by spraying natural hard water. Film was made by applying a pigment dispersion. To relate the ASTM 1- 5 scales to household usage we conducted a consumer “acceptance” test. Twenty four glasses with a wide range of deposits from various laboratory runs and including synthetically spotted and filmed glasses. The synthetic glasses had deposits that were typical of laboratory runs. Deposit amounts were related to concentration of applied so that the final scale would be linear with amount applied. The consumer test was run in the panelists dishwasher. There were 12 panelists. The glasses were loaded into the dishwasher rack. The panelist was requested to remove the glasses and put them away or set them aside for rewashing. Acceptance or rejection was recorded. Data from the 10 synthetic filmy and spotty was plotted on Pareto Charts which follow. From the charts we estimated the concentration at which all panelists would reject the glass as too spotty or filmy for use. This concentration was divided by four to give five levels of soil related to the ASTM Scale. ASTM 1No Deposit ASTM 225% of Unacceptable Level ASTM 350% of Unacceptable Level ASTM 475 % of Unacceptable Level ASTM 5100% of Unacceptable Level We are currently perfecting our techniques and measuring reproducibility. We plan to repeat the consumer study to confirm our initial results.

FILM ACCEPTABILITY vs AMOUNT OF PIGMENT

ACCEPTABILITY OF SPOTS VS NUMBER OF APPLICATIONS

Future Work Use the information about soil effects to conduct further performance evaluations Refine the procedures to produce sets of standard spotted and filmed glasses to use as standards to rate dishwashing performance.