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 DYING OF ARAMID FIBRES



    BY: MUDDASSAR HASSAN

       ROLL NO. 85
What are aramid fibers

 These are also called aromatic polyamides
 Those polyamides,which have aromatic six
  carbon rings in polymeric chain
Main types of aramid fibers
 Technora (made by Teijin of Japan)
 Conex (made by Teijin)
 Kevler (made by Dupont)
 Nomex (made by Dupont)
Good Qualities of fibers
 Good heat resistance
 High tenacity & modulus of rigidity
 Non flammability
 Greater sticking temperature
 Aramid dominate over glass fibers,and
  carbon fibers in all over the world market
 Stiffest &Toughest than even carbon and
  steel
 High modulus five times greater than
  polyester
 Excellent in tension
 Good chemical resistance
 Compactness and solidity of molecular
  structure
 In dry air,at 260C Aramid shrink only 2%
 By Sputter etching, depth of shade
  increased considerably
DISADVENTAGES
 No substantivity to dyes
 No environment friendly
 Poor UV resistance
 Rapid loss of strength with flexing ,folding
  &flogging
 Low light fastness,even spun dyed yarn
 Very expensive
 Poor in compression than glass
Main physical properties
 Melting poit371C
 Tenacity 5.3gmden at 65%RH&70F
 Specific gravity of fiber is 1.38
 Tg 275C
Dying of nomex with Basic dyes
 Fiber (2dtex50mm)
 Fabric form GSM (265gm
Washing
Nomex in fiber form are washed in Vald henriksen
   FBK MACHINE.
In fabric form,Walter Franke dying apparatus
Recipe for washing
 Nonionic surfactant 1gl
 Trisodiun phosphate dodecahydrate1gl
 Liqour ratio 30:1
 Washing condition
 Start at 40C &temperature raised to80C for 30
  min
 Rinsing with hot and cold for 10 min
Dying procedure
   Polycolor zeltex AG machine, used for dying
   Resipe
   Dye 2% o.w.f (Special dye, CI Basic 41)
   Sodium nitrate 20gl
   Career benzyl alcohol 70 gl
   Acetic acid 2.5gl (60%)
   Liqour ratio 20:1
After treatment process
 Materials are treated with 2gl nonionic
  surfectant for 20 min at 95C
 Acetic acid added to maintain PH to 3
 Hot &cold rinsing
 Fixation was carried out fir 30sec at 200C
Dyeing of Technora and conex with
          disperse dyes
Three commercial disperse dyes are used
1)Terasel yellow3GW(CI Disperse yellow54)
2)resolin red FB(CI Disperse Red 60)
3) Resolin blue FB (CI Disperse blue56)
DYING CONDITION
Temperature 190 &time 60 min
Dying machine
Mini –colour (Texam GIKEN)
Recipe
 Disperse dye (4-24%o.w.f)
 Dispersing agent (Disper VG) Nonionic
  surfectant 0.5gl
 Acetic acid 0.2gl & PH to4.2
 Liqour ratio15:1
 Dying temp is raised at 2degCmin
 Maintaining temp to 190C for 60 min
 Reduction clearing is carried out twice
Dyeing of Nomex type430filament
             yarn
   Three commercial basic dyes are use for dying
   CI Basic blue54 (CIBB-54)
   CI Basic red29 (CIBR-29)
   CI Basic redGL22(CIBR22)
 Dyeing Procedure
 Weight of skein of yarn(2.5)
 Infinite Liqour ratio140:1
 Commercial dyestuff (10% o.w.f)
 Using no career
 Temperature of dying range of 80 to 100C
Approaches to improve
    dyebility of aramid fibers
 More polar solvent
 Pretreatment of liquid ammonia
 Using benzyl alcohol as carrier
Pretreatment with liquid
              ammonia
 Pretreatment fibers with liquid
  ammonia,substantivity towards basic dye
  increase quite significantly
 Condition of pretreatment process
 Immersing 2.5g m-aramid in 100ml liquid
  ammonia
 Time 10 min &at 40 C
 Rinsing with hot and cold water
Dependence of light fastness properties on
       pretreatment & dyeing procedure
    CI Basic          fastness to light
                       A       B        C
   Yellow 28          3       3-4       4-5
   Orange 22          1       3         4
   Red46              1      2          3
   Red29              1       4         4-5
   Blue 49             1      3-4       3-4
   A : Without pretreatment, dyed without career
   B : Without pretreatment,dyed with 70 gl benzyl alcohol
   C : Pretretment with liquid ammonia,dyed without
    carrier
Conclusion
 Pretreatment of aramid fibers with liquid
  ammonia can not only increase substantivity for
  basic dyes,but also light fastness properties, as
  comparing with those of fibers dyed
  conventionally with basic dyes using career
  benzyl alcohol
Effect of polar solvent on dyebility of
                  aramid fiber
   These are three high polar solvents
   Dimethyl formamide
   Dimethyl acetate
   Dimethyl sulfoide

These solvents provide chemical energy to
  fibers,permitting rearrangement of the polymer
  chain through breakage and reformation of
  interchain hydrogen bonding
Factor of changing solvent diffusion in
                nomex fiber

 1)Molecular volume

Mol vol = Mol.wtr * 10 24N
Where r is density
N is Avogedro number
2)Temperature     of corresponding to onset of
  shrinkage.
Exhaust dyeing of treated
          nomex yarns
 Exhaustion of CIBB54 at 100C
 At 30 min
 Attaining max degree of structural modification
 Order of increasing exhaustion rate
 DMF<DMAc<DMSO
 In DMF,90% of dye liquor being exhausted after
  4hours
 In DMAc&DMSO leads to very rapid exhaustion
 95% of dye liquor being exhausted in 45 minutes
 Untreated yarns dyed according to commercial
  dying procedure in presence of Dymex career
  resulted in low exhaution45% of dye liquor
 Temperature dependence of exhaustion
  rate
 With DMF A slight decrease in rate occurs when
  treatment temperature decreases from 100 to 50C
 Considerable larger decrease in rate occurs on
  reducing temp of treatment to further to 40C
 With DMAc major change in exhaustion rate
  occurs between samples treated at 82.2&75C
Influence of treatment time on
        exhaustion rate
 An increase in treatment time, leads to faster
  exhaustion rate
 Temp from 30 sec to 30 min,solvent diffusion
 And polymer interaction are considerably faster
 But exhaustion rate is unaffected
 Structural modification changes also depends on
  treatment time
Conclusion
 Optimum condition of dying 100c and 30
  minutes then substrate is readily dyeable in
  atmosphere pressure
 After solvent treatment ,loss of polymer chain
  orientation and or formation of void takes place
 Solvent treated fabric leads to attain greater
  dyebility at expense of initial modulus and tensile
  strength
 Elimination of larger amount of careers
 Lower dyeing temperature and shorter dyeing
  time (significant benefit)
Effect of varying liquid ammonia pretreatment time
                          &dying temp
pretreatment        Dying        KS          Wash fast-
time                temp         VALUE        -ness
                    inC
0.2                 130          12.1         3-4
5                   130          12.4         3-4

10                  130          10.8         3-4

30                  130          11.0         3-4
30                  100          10.6         3-4
 Method of removing ammonia
 Rinsing
 Rinsing &drying
 Evaporation without rinsing
 Treatment        Tensile strength      Extension
  step              mNtex                (%)
  A                   270                 48
  B                   230                 64
  C                   213                 47
  D                  222                 27
  E                  243                 43
 A Raw fiber        B; Pretreatment 15 min in liquid
  ammonia
 C; Pretreated fiber dyed with basic dye D; Untreated fiber dyed with
  basic dye using benzyl alcohol E; Untreated fabric dyed with basic
  but without career( Effect of pretretment and dying method on fiber
  strength and extension)
Influence of sputter etching in
       shade of dyed fabrics
 The aramid fabric Technora dyed with CI
  Disperse54 etc, are treated by sputter etching and
  argon low-temperature plasma
 Sputter etching is effective I increasing color
  depth of dyed Technora
 As a decrease of L* for blue and red dyeing and
  considerable increase in C*for all three colors
 These effects on dyed Technora are slightly less
  with low temperature plasma treatment
 No significant effect on CONEX FABRIC
 Basic purpose of sputter etching is to
  produce deeper shade deeper and or more
  vivid colors on dyed aramid fabric without
  actually increasing concentration dye
 Technora caused by sputter etching is
  thought to be due to formation of
  Microcrates during treatment that severely
  restrict the reflection of incident light
 Name of device used for sputter etching,
  Shinku-kiku RFS-200
 Depth of shade is measured with colorEye
  MS2020 Spectrophotometer under illuminant
  D65 AND WITH 10 OBSERVER
 Spectrophotometer calculate value lightness L*
  and color difference E in CIELAB color space
 CONDITION OF SPUTTER ETCHING
 Pressure of 20 pa
 Power rating of 100 Wt
 Time of treatment from 30 to 300sec
References
 JSDC Volume111 Mach 1995,page72
 JSDC Volume 111 March 1995 ,page 111
 TRJ April 1986, page 254
 JSDC Volume 110 JulyAug , page228,1994
 Encyclopedia of textile finishing by
  H.K.ROUETTE
 Man made fibers, page408 By R.W.Moncrieff
 www.dupont product.com

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Dyeing of aramid fibers

  • 1.  DYING OF ARAMID FIBRES BY: MUDDASSAR HASSAN ROLL NO. 85
  • 2. What are aramid fibers  These are also called aromatic polyamides  Those polyamides,which have aromatic six carbon rings in polymeric chain
  • 3. Main types of aramid fibers  Technora (made by Teijin of Japan)  Conex (made by Teijin)  Kevler (made by Dupont)  Nomex (made by Dupont)
  • 4. Good Qualities of fibers  Good heat resistance  High tenacity & modulus of rigidity  Non flammability  Greater sticking temperature  Aramid dominate over glass fibers,and carbon fibers in all over the world market  Stiffest &Toughest than even carbon and steel
  • 5.  High modulus five times greater than polyester  Excellent in tension  Good chemical resistance  Compactness and solidity of molecular structure  In dry air,at 260C Aramid shrink only 2%  By Sputter etching, depth of shade increased considerably
  • 6. DISADVENTAGES  No substantivity to dyes  No environment friendly  Poor UV resistance  Rapid loss of strength with flexing ,folding &flogging  Low light fastness,even spun dyed yarn  Very expensive  Poor in compression than glass
  • 7. Main physical properties  Melting poit371C  Tenacity 5.3gmden at 65%RH&70F  Specific gravity of fiber is 1.38  Tg 275C
  • 8. Dying of nomex with Basic dyes  Fiber (2dtex50mm)  Fabric form GSM (265gm Washing Nomex in fiber form are washed in Vald henriksen FBK MACHINE. In fabric form,Walter Franke dying apparatus
  • 9. Recipe for washing  Nonionic surfactant 1gl  Trisodiun phosphate dodecahydrate1gl  Liqour ratio 30:1  Washing condition  Start at 40C &temperature raised to80C for 30 min  Rinsing with hot and cold for 10 min
  • 10. Dying procedure  Polycolor zeltex AG machine, used for dying  Resipe  Dye 2% o.w.f (Special dye, CI Basic 41)  Sodium nitrate 20gl  Career benzyl alcohol 70 gl  Acetic acid 2.5gl (60%)  Liqour ratio 20:1
  • 11. After treatment process  Materials are treated with 2gl nonionic surfectant for 20 min at 95C  Acetic acid added to maintain PH to 3  Hot &cold rinsing  Fixation was carried out fir 30sec at 200C
  • 12. Dyeing of Technora and conex with disperse dyes Three commercial disperse dyes are used 1)Terasel yellow3GW(CI Disperse yellow54) 2)resolin red FB(CI Disperse Red 60) 3) Resolin blue FB (CI Disperse blue56) DYING CONDITION Temperature 190 &time 60 min Dying machine Mini –colour (Texam GIKEN)
  • 13. Recipe  Disperse dye (4-24%o.w.f)  Dispersing agent (Disper VG) Nonionic surfectant 0.5gl  Acetic acid 0.2gl & PH to4.2  Liqour ratio15:1  Dying temp is raised at 2degCmin  Maintaining temp to 190C for 60 min  Reduction clearing is carried out twice
  • 14. Dyeing of Nomex type430filament yarn  Three commercial basic dyes are use for dying  CI Basic blue54 (CIBB-54)  CI Basic red29 (CIBR-29)  CI Basic redGL22(CIBR22)  Dyeing Procedure  Weight of skein of yarn(2.5)  Infinite Liqour ratio140:1  Commercial dyestuff (10% o.w.f)
  • 15.  Using no career  Temperature of dying range of 80 to 100C
  • 16. Approaches to improve dyebility of aramid fibers  More polar solvent  Pretreatment of liquid ammonia  Using benzyl alcohol as carrier
  • 17. Pretreatment with liquid ammonia  Pretreatment fibers with liquid ammonia,substantivity towards basic dye increase quite significantly  Condition of pretreatment process  Immersing 2.5g m-aramid in 100ml liquid ammonia  Time 10 min &at 40 C  Rinsing with hot and cold water
  • 18. Dependence of light fastness properties on pretreatment & dyeing procedure  CI Basic fastness to light  A B C  Yellow 28 3 3-4 4-5  Orange 22 1 3 4  Red46 1 2 3  Red29 1 4 4-5  Blue 49 1 3-4 3-4  A : Without pretreatment, dyed without career  B : Without pretreatment,dyed with 70 gl benzyl alcohol  C : Pretretment with liquid ammonia,dyed without carrier
  • 19. Conclusion  Pretreatment of aramid fibers with liquid ammonia can not only increase substantivity for basic dyes,but also light fastness properties, as comparing with those of fibers dyed conventionally with basic dyes using career benzyl alcohol
  • 20. Effect of polar solvent on dyebility of aramid fiber  These are three high polar solvents  Dimethyl formamide  Dimethyl acetate  Dimethyl sulfoide These solvents provide chemical energy to fibers,permitting rearrangement of the polymer chain through breakage and reformation of interchain hydrogen bonding
  • 21. Factor of changing solvent diffusion in nomex fiber  1)Molecular volume Mol vol = Mol.wtr * 10 24N Where r is density N is Avogedro number 2)Temperature of corresponding to onset of shrinkage.
  • 22. Exhaust dyeing of treated nomex yarns  Exhaustion of CIBB54 at 100C  At 30 min  Attaining max degree of structural modification  Order of increasing exhaustion rate  DMF<DMAc<DMSO  In DMF,90% of dye liquor being exhausted after 4hours  In DMAc&DMSO leads to very rapid exhaustion  95% of dye liquor being exhausted in 45 minutes
  • 23.  Untreated yarns dyed according to commercial dying procedure in presence of Dymex career resulted in low exhaution45% of dye liquor  Temperature dependence of exhaustion rate  With DMF A slight decrease in rate occurs when treatment temperature decreases from 100 to 50C  Considerable larger decrease in rate occurs on reducing temp of treatment to further to 40C  With DMAc major change in exhaustion rate occurs between samples treated at 82.2&75C
  • 24. Influence of treatment time on exhaustion rate  An increase in treatment time, leads to faster exhaustion rate  Temp from 30 sec to 30 min,solvent diffusion  And polymer interaction are considerably faster  But exhaustion rate is unaffected  Structural modification changes also depends on treatment time
  • 25. Conclusion  Optimum condition of dying 100c and 30 minutes then substrate is readily dyeable in atmosphere pressure  After solvent treatment ,loss of polymer chain orientation and or formation of void takes place  Solvent treated fabric leads to attain greater dyebility at expense of initial modulus and tensile strength  Elimination of larger amount of careers
  • 26.  Lower dyeing temperature and shorter dyeing time (significant benefit)
  • 27. Effect of varying liquid ammonia pretreatment time &dying temp pretreatment Dying KS Wash fast- time temp VALUE -ness inC 0.2 130 12.1 3-4 5 130 12.4 3-4 10 130 10.8 3-4 30 130 11.0 3-4 30 100 10.6 3-4
  • 28.  Method of removing ammonia  Rinsing  Rinsing &drying  Evaporation without rinsing  Treatment Tensile strength Extension  step mNtex (%)  A 270 48  B 230 64  C 213 47  D 222 27  E 243 43  A Raw fiber B; Pretreatment 15 min in liquid ammonia  C; Pretreated fiber dyed with basic dye D; Untreated fiber dyed with basic dye using benzyl alcohol E; Untreated fabric dyed with basic but without career( Effect of pretretment and dying method on fiber strength and extension)
  • 29. Influence of sputter etching in shade of dyed fabrics  The aramid fabric Technora dyed with CI Disperse54 etc, are treated by sputter etching and argon low-temperature plasma  Sputter etching is effective I increasing color depth of dyed Technora  As a decrease of L* for blue and red dyeing and considerable increase in C*for all three colors  These effects on dyed Technora are slightly less with low temperature plasma treatment
  • 30.  No significant effect on CONEX FABRIC  Basic purpose of sputter etching is to produce deeper shade deeper and or more vivid colors on dyed aramid fabric without actually increasing concentration dye  Technora caused by sputter etching is thought to be due to formation of Microcrates during treatment that severely restrict the reflection of incident light
  • 31.  Name of device used for sputter etching, Shinku-kiku RFS-200  Depth of shade is measured with colorEye MS2020 Spectrophotometer under illuminant D65 AND WITH 10 OBSERVER  Spectrophotometer calculate value lightness L* and color difference E in CIELAB color space  CONDITION OF SPUTTER ETCHING  Pressure of 20 pa  Power rating of 100 Wt  Time of treatment from 30 to 300sec
  • 32. References  JSDC Volume111 Mach 1995,page72  JSDC Volume 111 March 1995 ,page 111  TRJ April 1986, page 254  JSDC Volume 110 JulyAug , page228,1994  Encyclopedia of textile finishing by H.K.ROUETTE  Man made fibers, page408 By R.W.Moncrieff  www.dupont product.com