Belinda Tomasi

Daniel Huff
Final Project Report
IEE 572 Design of Engineering Experiments
December 4, 2000
1. Recognition and Statement of Problem
!romic acid !as been used for decades "it!in industr# to treat metal surfaces$ T"o
common applications in%ol%ing c!romic acid !a%e been& '( to increase t!e corrosion
resistance of a metal surface and 2( to prepare a metal surface for ad!esi%e bonding$
)lt!oug! processes suc! as t!ese !a%e been %er# useful in industr# and !a%e been used
for decades, c!romic acid possesses !exa%alent c!romium, "!ic! is no" *no"n to be a
carcinogen$ T!erefore, in recent #ears, t!ere !as been significant effort to find alternati%e
processes t!at can be used in place of c!romium+containing processes$
,or non+ad!esi%e bonding applications in%ol%ing aluminum surfaces, t!e use of an
alternati%e, sulfuric acid+based replacement process !as been used successfull# for t!e
past decade$ )lt!oug! t!is process produces an aluminum oxide la#er "it! corrosion
resistance properties comparable to t!ose of t!e c!romic acid process, t!is oxide la#er
does not possess comparable ad!esion properties$ T!erefore, t!e sulfuric acid+based
process cannot be used in place of t!e c!romic acid %ersion for critical ad!esi%e bonding
applications$
Electrol#tic, p!osp!oric acid based treatments are *no"n to -open up. t!e outer surface
in aluminum allo#s and t!e open nature of t!e surface can impro%e ad!esion properties$
/ne of t!ese p!osp!oric acid based processes !as been used successfull# as a deoxidi0er
pretreatment process1 !o"e%er, t!is deoxidi0er process "as de%eloped as a pretreatment
for a different anodi0e process and !as generall# not been used as a pretreatment for t!e
sulfuric acid based anodi0e process described abo%e$ ,urt!ermore, sulfuric acid is
strongl# acidic, and opening up t!e surface ma# lead to a retention of sulfuric acid$ T!is
residual acidit# mig!t interfere "it! t!e curing mec!anisms of ad!esi%e and primers,
t!ereb# reducing o%erall ad!esion properties$
To counter t!e effects caused b# possible residual acidit#, t!e use of a bicarbonate,
neutrali0ing dip after t!e sulfuric acid process can be emplo#ed$ T!is surface
neutrali0ation tec!ni2ue !as been used successfull# in ot!er industrial processes
in%ol%ing strong acids$
,inall#, t!e application of certain silicon+based coupling agents !as been *no"n to
impro%e ad!esion and ot!er properties on %arious inorganic materials$ ertain titanium,
0irconium, and aluminum+based c!emicals !a%e also been used, sometimes in
con3unction "it! t!e silicon+based coupling agents$
B# combining t!e sulfuric acid based anodi0e process "it! t!e deoxidi0er pretreatment,
t!e neutrali0er post treatment, and t!e application of ad!esion promoting coupling agents,
preliminar# ad!esion studies !a%e s!o"n excellent ad!esion properties under most test
conditions$ Ho"e%er, results of tests performed at cold temperatures 4+55
o
,( !a%e
ex!ibited extreme %ariabilit#1 in some instances, cold temperature results "ere %er# poor$
2
Due to t!ese poor results at lo" temperature, it "as decided to perform a designed
experiment on t!is combination process to determine if parameters could be ad3usted to
impro%e cold temperature ad!esion properties$
2. Choice of factors, levels and ranges
In creating t!is combination process, note t!at t!e %arious indi%idual steps ++ t!e
deoxidi0er pretreatment, t!e sulfuric acid based anodi0e process, t!e bicarbonate
neutrali0ation step, and t!e application of a coupling agent treatment ++ "ere extracted
from ot!er processes$ T!ese indi%idual procedures !ad not pre%iousl# been used in
combination "it! eac! ot!er$ onse2uentl#, in t!e preliminar# studies in%ol%ing t!is
combination of process factors 4prior to t!is designed experiment(, le%els of t!e
indi%idual factors "ere set at t!e standard %alues normall# used in t!e ot!er processes$
,or t!is designed experiment, t!e center points "ere assumed to be t!ese same standard
le%els, and lo" and !ig! points "ere selected from eac! side of t!e center points$
In t!is experiment, parameters related to t!e sulfuric acid anodi0e "ere not %aried since
t!is process must meet ot!er re2uirements 4e$g$, corrosion resistance(, and %ariation of t!e
parameters related to t!is process mig!t affect t!ose properties$ Ho"e%er, factors related
to t!e ot!er t!ree process steps 4t!e deoxidi0er, t!e neutrali0ation, and t!e coupling agent
application steps( "ere %aried and are s!o"n in T)B6E I$
TA!" #. $escriptions of "%perimental Factors.
Factor $escription
&ain
Factor
$esignation
!o'
!evel
()*
Center
Point
+igh
!evel
(,*
Time used in p!osp!oric acid+based
pretreatment process 4prior to sulfuric
acid process(
) 7 min '0 min '7 min
8oltage used in p!osp!oric acid+based
pretreatment process 4prior to sulfuric
acid process(
B 5 %olts 7$5 %olts '0 %olts
oncentration of sodium bicarbonate
neutrali0ing solution 4used after
sulfuric acid+based process(
2$09 5$09 :$09
Time soa*ing in sodium bicarbonate
neutrali0ing solution 4used after
sulfuric acid+based process(
D 5 sec 55 sec '05 sec
)mount of silicon+based coupling
agent in ad!esion+promoting solution
E 5 ml '0 ml '5 ml
)mount of 0irconium+based coupling
agent in ad!esion+promoting solution
, 2$5 ml 5$0 ml 7$5 ml
Immersion time of panel in mixed
4silicon;0irconium( coupling agent
< 70 sec '20
seconds
2'0 sec
7
solution
4
-. Selection of the Response .ariable
)s mentioned abo%e, "e !a%e pre%iousl# obtained good ad!esion results on sulfuric acid
processed surfaces b# using t!e p!osp!oric acid deoxidi0er pretreatment and b# using
bicarbonate neutrali0ing bat! and organosilane+based coupling agent treatments as post
treatments$ Ho"e%er, "e !a%e !ad extreme %ariabilit# of our ad!esion results "!en t!ese
surfaces "ere tested under cold conditions$ =ince acceptable ad!esion properties at cold
temperature !a%e been difficult to obtain, t!is experiment specificall# focused upon t!e
ad!esion peel strengt! 4using a standard, )=T> D 7'57 test procedure( performed under
cold temperature conditions 4+55
o
,($
/. Choice of "%perimental $esign
T!e experiment "as performed using a 2
7+7
fractional factorial design 4?esolution I8( in
t"o confounded bloc*s, as s!o"n in T)B6E II belo"$ T"ent# total runs "ere
performed, "it! eac! bloc* of ten runs performed on a separate da#$ 4) -run. is defined
in t!e next section$( Bloc*s "ere defined b# t!e sign of t!e )BD interaction term$
@it!in eac! bloc*, runs "ere performed in random order, except for t!e first and last run
of eac! da#Abloc*, "!ic! "ere center point runs$
TA!" ##. "%perimental $esign.
?un
ID B ) B D
E C
)B
, C
BD
< C
)D
Block
=ABD
Run
Order
Day #1
Run
Order
Day #2
' + + + + + + + + 5
2 ; + + + ; + ; ; 4
7 + ; + + ; ; + ; :
4 ; ; + + + ; ; + 4
5 + + ; + ; ; ; + 7
5 ; + ; + + ; + ; 5
7 + ; ; + + + ; ; 7
: ; ; ; + ; + + + '
D + + + ; + ; ; ; 7
'0 ; + + ; ; ; + + 2
'' + ; + ; ; + ; + D
'2 ; ; + ; + + + ; D
'7 + + ; ; ; + + ; 2
'4 ; + ; ; + + ; + :
'5 + ; ; ; + ; + + 5
'5 ; ; ; ; ; ; ; ; 5
'7 0 0 0 0 0 0 0 '
': 0 0 0 0 0 0 0 '0
'D 0 0 0 0 0 0 0 '
5
20 0 0 0 0 0 0 0 '0
0. Performing the "%periment
In t!is experiment, a -run. consisted of t!e treatment of one E0$025. x 4. x D. aluminum
panelF and one E0$057. x 4. x :. aluminum panelF processed toget!er at t!e appropriate
factor le%els s!o"n in t!e table abo%e$ T!ese t"o panels "ere t!en bonded toget!er "it!
an ad!esi%e and cut longitudinall# into t!ree '."ide strips$ Gsing a mec!anical test "it!
temperature+controlled c!amber set to H55
o
,, eac! '. "ide strip "as tested b# positioning
in a separating, roller+t#pe apparatus, "!ic! "as placed inside a cold 4+55
o
,( test c!amber
and attac!ed to mec!anical test mac!ine grips$ )fter a '0+minute soa* period at H55
o
,,
t!e specimen "as peeled apart in t!e cold c!amber using a constant speed of motion, and
t!e a%erage force re2uired to peel t!e specimen apart "as determined$ T!is a%erage %alue
is called t!e -peel strengt!. of t!e specimen, "it! units of Epounds per inc! "idt!F$
@it! t"ent# runs and t!ree specimens per run, sixt# indi%idual peel strengt! specimens
"ere generated and tested$ =ince it "as not possible to test all t!ese specimens "it!in a
single time period, testing "as performed on t!ree separate da#s$ T!e t!ree specimens
obtained from eac! run "ere separated into t!ree different test groups, and eac! group of
t"ent# specimens "as tested on a different da# in random order$
T!erefore, for eac! run, t!e a%erage of t!e t!ree test specimens 4tested on separate da#s(
"as t!e response %ariable for t!e run$

=ufficient planning, preparation and care "ere used prior to and during t!e experiment so
problems could be a%oided, and fortunatel#, no significant problems "ere encountered
during t!e experiment$ T!e run c!art used during t!is experiment is s!o"n in ,igure '$
5
Fig1re 1. R1n Chart 2sed d1ring "%periment.
7
Factors A, B, C, D, E, F & G to be varied as follows
Day 1
Run
Order
Std.
Alkaline
Clean
Deox.
A (H
3
PO
4
pretreatment
soak time)
Deox.
B (H
3
PO
4
pretreatment
olta!e)
"SAA
Anodi#e
(1$%)
&eutrali#ation
C (&aHCO
3
'on'.)
&eutrali#ation
D (&aHCO
3
soak time)
Couplin! A!ents
E & F (amount o( 'ouplin!
a!ents)
Couplin! A!ents
G ('ouplin! a!ent
soak time)
Apply
"ond
Primer
1 $ min 1) min. *.$ % +) min $, $$ se'. (1) 1) m- Si . $ m- /r 10) se'. 113 mil
+ 2 13 min. $ % 2 +, 1)$ se'. (2) 1$ m- Si . *.$ m- /r 3) se'. 2
3 2 13 min. 1) % 2 0, $ se'. (3) 1$ m- Si . +.$ m- /r 3) se'. 2
4 2 13 min. 1) % 2 +, $ se'. (4) $ m- Si . *.$ m- /r 3)) se'. 2
$ 2 * min. 1) % 2 0, 1)$ se'. (4) $ m- Si . *.$ m- /r 3) se'. 2
3 2 * min. $ % 2 +, $ se'. (5) $ m- Si . +.$ m- /r 3) se'. 2
* 2 * min. $ % 2 0, $ se'. (2) 1$ m- Si . *.$ m- /r 3)) se'. 2
0 2 13 min. $ % 2 0, 1)$ se'. (5) $ m- Si . +.$ m- /r 3)) se'. 2
4 2 * min. 1) % 2 +, 1)$ se'. (3) 1$ m- Si . +.$ m- /r 3)) se'. 2
1) 2 1) min. *.$ % 2 $, $$ se'. (1) 1) m- Si . $ m- /r 10) se'. 2
Day +
Run
Order
1 $ min 1) min. *.$ % +) min $, $$ se'. (1) 1) m- Si . $ m- /r 10) se'. 113 mil
+ 2 * min. $ % 2 0, 1)$ se'. (3) 1$ m- Si . +.$ m- /r 3) se'. 2
3 2 * min. 1) % 2 0, $ se'. (5) $ m- Si . +.$ m- /r 3)) se'. 2
4 2 13 min. $ % 2 +, $ se'. (3) 1$ m- Si . +.$ m- /r 3)) se'. 2
$ 2 13 min. $ % 2 0, $ se'. (4) $ m- Si . *.$ m- /r 3) se'. 2
3 2 13 min. 1) % 2 0, 1)$ se'. (2) 1$ m- Si . *.$ m- /r 3)) se'. 2
* 2 * min. $ % 2 +, 1)$ se'. (4) $ m- Si . *.$ m- /r 3)) se'. 2
0 2 * min. 1) % 2 +, $ se'. (2) 1$ m- Si . *.$ m- /r 3) se'. 2
4 2 13 min. 1) % 2 +, 1)$ se'. (5) $ m- Si . +.$ m- /r 3) se'. 2
1) 2 1) min. *.$ % 2 $, $$ se'. (1) 1) m- Si . $ m- /r 10) se'. 2
3. Statistical Anal4sis of the $ata
Experimental test results are s!o"n in T)B6E III$
TA!" ###. "%perimental Res1lts5 )30
o
F Peel Test.
?un ID B
Test B'
4test da# '(
Test B2
4test da# 2(
Test B7
4test da# 7(
)%erage Ieel
=trengt! 4pi"(
=tandard
De%iation
4pi"(
' 7$7 5$4 D$0 7$77 '$:2
2 25$4 25$' 70$4 27$0 2$D:
7 25$0 27$7 25$5 25$7 '$'7
4 ':$5 :$5 ''$' '2$7 5$'5
5 24$4 '4$4 24$7 2'$2 5$:5
5 25$4 '5$7 24$D 22$5 5$45
7 27$: 25$D 72$4 2:$7 7$74
: 'D$: '7$D 2'$5 'D$7 '$:0
D 27$' 27$4 77$7 2D$7 7$2:
'0 ''$7 7$0 '4$4 '0$D 7$72
'' 'D$D :$2 ':$: '5$5 5$45
'2 25$: 27$D 25$D 25$5 '$52
'7 25$7 20$D 25$2 24$' 2$:4
'4 '7$7 '5$5 '5$0 '5$D '$2'
'5 20$' 'D$5 27$0 20$D '$:4
'5 77$0 2:$5 40$5 75$4 5$'5
'7 D$D '5$0 D$7 ''$4 7$'7
': '0$5 :$: '7$2 '0$D 2$2'
'D 2D$2 'D$D 'D$' 22$7 5$5'
20 2'$5 '7$2 ':$5 'D$' 2$'D
:
Design Expert =oft"are "as used to anal#0e t!e data$ Jormal probabilit# plots "ere
used to select possible significant factors and interactions$ )fter selecting a combination
of main factors and t"o factor interactions, Design Expert "as used to perform an
)J/8) anal#sis of t!e data and to generate %arious measures of model ade2uac#$
T)B6E I8 s!o"s se%eral main factor and interaction combinations "it! corresponding
model ade2uac# measurement %alues$
TA!" #.. &odel Ade61ac4 &eas1res of .ario1s &odel Combinations.
Based upon t!e model ade2uac# %alues s!o"n in T)B6E I8, t!e model
EB,,D,E,,,<,B,B<,,F appears to be t!e best model$ In t!is model, main effect )
4Deoxidi0er time( does not appear to be significant$ )fter remo%ing ,actor ), t!e
experiment pro3ects into a 2
7+2
design 4also ?esolution I8($ )ssuming 7+factor
interactions are insignificant, t!is frees t!e B and B< 2+factor interactions from ot!er
aliases 4alt!oug! t!e 2+factor interaction , is still aliased "it! anot!er 2+factor
interaction, E<($
D
Cobi!atio!
" of #ers
i! $odel
$odel
%&'al(e
)ac* of Fit
%&'al(e +&,-(ared
Ad./
+&
,-(ared
%red/
+&,-(ared
C(rvat(re
%&'al(e
"5 C5 65 75 "7 $ ).)))3 ).43+3 ).0)33 ).*+13 ).$*34 ).)))0
"5 C5 65 85 75 "7 3 ).)))$ ).$331 ).0$+4 ).**14 ).31*$ ).)))$
"5 C5 D5 65 85 75 "7 * ).)))3 ).$0*$ ).0043 ).0)33 ).33*3 ).)))4
"5 C5 65 85 75 "C5 "7 * ).)))3 ).3$00 ).4)+$ ).0343 ).*)$* ).)))+
A5 "5 C5 65 85 75 "7 * ).))13 ).444$ ).0$$4 ).*$4+ ).$+4$ ).)))0
"5 C5 D5 65 85 75 "C5 "7 0 ).)))+ ).**00 ).4344 ).0*31 ).*0)4 9).)))1
B, C, D, E, F, G, BC, BG, CF 0 1/1113 1/2222 1/0435 1/2225 1/2134 1/1111
All 8a'tors : ;ntera'tions 1$ ).13)) 111 ).4**) ).0)4* &<A ).)334
)ssuming , 4and not E<( is t!is 2+factor interaction, t!e e2uation for t!is model is&
+55
o
, peel strengt! C 7$:'742 ; '$0D'424B( H 0$57D5:4( ; 0$0'52754D( ; 0$2'5504E(
; 0$052:774,( ; 0$05D'554<( ; 0$'27574B( H 0$005D'254B<(
; 0$0557774,(
"!ere& B C deoxidi0er %oltage
C bicarbonate concentration
D C bicarbonate soa* time
E C silicon+based coupling agent concentration
, C 0irconium additi%e concentration
< C soa* time in coupling agent solution
B C 2+factor interaction bet"een B and
B< C 2+factor interaction bet"een B and <
, C 2+factor interaction bet"een and ,
)dditional experimentation could be performed to free t!e ,CE< alias1 !o"e%er, ot!er
considerations s!ould be explored furt!er before committing more time and effort to t!e
next experiment$ ,or example, t!e anal#ses indicate t!at t!e use of !ig!er order terms or
data transformations s!ould possibl# be considered in c!aracteri0ing t!e model$ T!e
cur%ature I+%alues s!o"n in T)B6E I8 indicate a lo" probabilit# t!at t!e cur%ature is
not present 4i$e$, t!ese %alues indicate a !ig! probabilit# t!at cur%ature is present($
,urt!ermore, man# of t!e residuals %s$ main factor plots 4e$g$, residuals %s$ deoxidi0er
%oltage, residuals %s$ bicarbonate soa* time, residuals %s$ silane coupling agent
concentration, and residuals %s$ coupling agent soa* time( indicate a slig!t -coning.
effect$ )not!er interesting fact is t!at if t!e mean of t!e four center point runs is
compared "it! t!e mean of t!e ot!er sixteen +A; le%el runs and also "it! t!e !ig!est %alue
of all t!e runs, t!e follo"ing differences are obser%ed&
mean %alue of center point runs& '5$0 pi"
mean %alue of all ot!er runs& 2'$4 pi"
!ig!est %alue 4?un B'5(& 75$4 pi"
?ecall t!at t!e center point le%els of t!e different factors are t!e le%els used "!en t!ese
indi%idual procedures are used in t!eir more+traditional roles as part of ot!er processes$
It "as initiall# assumed "!en t!ese factors "ere combined for t!e ne" process discussed
in t!is report, t!e same standard le%els 4as used in ot!er processes( s!ould also be used to
obtain t!e best peel strengt! %alues$ Ho"e%er, in comparing t!e %alues abo%e, it is
ob%ious t!ese standard le%els do not gi%e optimum results for t!is ne" process$ @it!in
t!e combinations of factors and le%els t!at "ere performed "it!in t!is experiment, t!e
!ig!est response %alue 4s!o"n abo%e, from ?un B'5( "as obtained "!en all factors "ere
set at t!eir !ig! 4;( le%el$ T!is is enlig!tening as to "!# suc! poor results "ere obser%ed
in preliminar# studies of t!is process 4prior to t!is designed experimental stud#($
'0
T!erefore, before additional experiments are carried out to define t!e model furt!er,
certain response surface met!ods s!ould be performed to determine if factor le%els are
e%en "it!in t!e %icinit# of t!eir optimum le%els$
Bloc* effects
T!e center point runs "ere performed as t!e first and last run of eac! da#Abloc*, and t!e
test results of t!ese runs indicate a significant bloc* effect&
Ieel strengt!, center point run B'+' 4da# B', 'st run(& ''$4 pi"
Ieel strengt!, center point run B'+'0 4da# B', last run(& '0$D pi"
Ieel strengt!, center point run B2+' 4da# B2, 'st run(& 22$7 pi"
Ieel strengt!, center point run B2+'0 4da# B2, last run(& 'D$' pi"
T!erefore, t!e inclusion t!e t"o confounded bloc*s "it!in t!e experimental design "as
beneficial for t!e anal#sis of t!e data$ Jote t!at "it!in eac! bloc*, t!ere is good
agreement bet"een t!e results of t!e t"o center point runs$
?esiduals plots&
)lt!oug! se%eral of t!e residuals %s$ factor le%el plots ex!ibited a -coning. effect, and
alt!oug! t!ere appeared to be a bloc* effect bet"een t!e '
st
and 2
nd
da#, ot!er residual
plots did not ex!ibit an# strange patterns$ T!ese include&
Jormal probabilit# plot of t!e residuals
?esiduals %s$ predicted %alues
?esiduals %s$ run order
T!e Design Expert )J/8) anal#sis and t!e %arious plots mentioned abo%e are attac!ed
in t!e )IIEJDIK$
''
7. Concl1sions and Recommendations
B# performing t!is experiment and stud#ing %arious factors related to t!e ad!esion
strengt! of anodi0ed surfaces, an excellent model 4e$g$, ?
2
C0$D4:1 ad3usted ?
2
C0$::D(
"as de%eloped$ T!e e2uation of t!is model is&
+55
o
, peel strengt! C 7$:'742 ; '$0D'424B( H 0$57D5:4( ; 0$0'52754D(
; 0$2'5504E( ; 0$052:774,( ; 0$05D'554<(
; 0$'27574B( H 0$005D'254B<( ; 0$0557774,(
"!ere& B C deoxidi0er %oltage
C bicarbonate concentration
D C bicarbonate soa* time
E C silicon+based coupling agent concentration
, C 0irconium additi%e concentration
< C soa* time in coupling agent solution
B C 2+factor interaction bet"een B and
B< C 2+factor interaction bet"een B and <
, C 2+factor interaction bet"een and ,
)lt!oug! t!e experiment and anal#sis "as able to create an excellent model, t!e anal#ses
s!o"ed !ig!er order terms and data transformations mig!t be useful in c!aracteri0ing t!e
model furt!er$
enter point le%els, "!ic! "ere assumed to be t!e initial best estimates for optimum
factor le%els, "ere s!o"n to produce poor results$ T!is agrees "it! t!e !ig! %ariabilit#
and poor results obser%ed in preliminar# studies of t!is process prior to t!is designed
experiment, in "!ic! onl# t!e center point le%els "ere used to perform t!e process$
@it!in t!e combinations of factors and le%els t!at "ere performed in t!is experiment, t!e
!ig!est response %alue "as obtained "!en all factors "ere set at t!eir !ig! 4;( le%el$
T!e use of t"o confounded bloc*s "it!in t!e experimental design "as !elpful in
accounting for t!e effect of t!e particular da# in "!ic! runs "ere performed$
?esponse surface met!ods "ould be useful for determining if t!e factors are in t!eir
optimum region and for performing general optimi0ation of t!is process$
'2
APP"8$#9
Design Expert )J/8) anal#sis
?esidual Ilots
/ne factor at a time and interaction grap!s
'7