Platzhalter Titelbild

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F

F

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Organomodified Siloxanes

for High Filled

HFFR Cable Compounds

Seite | 2

What are Organomodified

Siloxanes (OMS)?

� Organomodified siloxanes (OMS) are performance

additives to improve surface and bulk properties

� They overcome the disadvantages of silicone oil by

introduction of organic groups on the silicone

backbone

� They generate a permanent functionalization of

thermoplastic polymers

� Depending on the modification. OMS can orientate

to the surface (also internal surfaces) and/or to the

bulk phase of the polymer

� OMS enhances processing. surface and material

properties

Seite | 3

Different Flame Retardants in

Thermoplastics and Mode of Action

Antimony trioxide +

brominated substances

Organic or inorganic

phosphorous substances

Metal hydroxides or

carbonates

Nitrogen containing

substances

Plastics with inherent flame

retardant characteristics

Formation of radicals which block the

flame reaction

Flame reaction is stopped by

formation of polyphosphoric acid

Formation of not flammable gas

water or carbon dioxide

Formation of not flammable gas

nitrogen oxides

Polysulfone. Polyether sulfones.

Polyaryl ether ketones

Seite | 4

Mechanism of HFFR Fillers

Thermal Dekomposition of MDH or ATH

Due to thermal decomposition MDH and ATH will form inorganic oxides and water.

The higher decomposition temperature of MDH easies the processing.

Source: Functional Fillers for Plastics. Marino Xanthos

2 Al(OH)3 → Al2O3 + 3H2O

Mg(OH)2 → MgO + H2O

Seite | 5

Recommended Products

for HFFR Compounds

� Liquid. solvent free organomodified siloxane

� Reactive OMS therefore suitable for peroxide curing systems

� Designed for high filled thermoplastic HFFR cable compounds

based on polyolefin. EVA. x-PP. x-PE as well as for EPDM

� Recommended Dosage: 0.5 % - 2.0 % on compound

� TEGOMER® V-Si 4042

� TEGOMER® FR 100

� Solid organomodified siloxane compound

� Especially developed for HFFR Cable Compounder. which

prefer using non liquid additives

� Suitable for polyolefin. EVA. x-PP. x-PE and EPDM

� Recommended Dosage: 1.0 % - 3.0 % on compound

Seite | 6

Recommended Products

for HFFR Compounds

� TEGOPREN® 6875

� Liquid organomodified siloxane

� Used as post treatment for fillers to create easy to disperse grades of HFFR fillers

� Used as an universal drawing oil for wire drawing and to reduce “peel off” forces in

cable insulating materials. e.g. CPE. Rubber. PVCC.

� TEGOPREN® 5885

� Liquid. solvent free organomodified siloxane

� Designed for high filled thermoplastic HFFR cable compounds

� Also recommended for nano clay containing compounds

� Suitable for polyolefin. EVA. x-PP. x-PE and EPDM

� Recommended Dosage: 0.5 % - 2.0 % on compound

+ +

OMS Exfoliated primary clay

particles in polymer

Clay PolymerOMS coated

clay

Seite | 7

Which Additive Meets which

Type of Customer

HFFR Producer HFFR

Compounder

HFFR Cable

Manufacture

TEGOPREN® 6875

TEGOPREN® 6875-45

Production of inorganic

Fillers for flame retardant

application like ATH. AMH.

MDH. nano Clays.

CarbonatesC.

Used for the surface

treatment

TEGOMER® V-Si 4042

TEGOMER® FR 100

TEGOMER® 5885

Production and

development of

compounds

Dispersing of filler with

high loadings.

Improvement of

mechanical. surface

and FR properties

TEGOPREN® 6875

TEGOMER® V-Si 4042

TEGOMER® FR 100

TEGOMER® 5885

Processing of cable

extrusion and or wire

drawing

Processing aid and

dispersant.

Lubricant for wire

drawing

Seite | 8

Additive Technologies used in HFFR

Cable Application

OOO

OH

Si

O

OR

ORAl(OH)3

ATH or MDH

particles

Al(OH)3

ATH or MDH

particlesOH

OH

HO

HO

Silanes or maleinic acid

anhydride grafted polymers

are used to interact with

hydroxy functional

flame retardants

Silicone oil is an external

lubricant only

OMS can interact with

Polymers and FR. adjusted

functionalisation is possible

Seite | 9

How to Use TEGOMER® in the

Processing

Heating elements

Motor

HopperMotor

I. During compounding with

kneader or double screw extruders

II. During cable extrusion

1. Fast Wetting

� Allows higher processing speed

� Allows higher loadings

2. Enhanced Grinding

� Perfect distribution of HFFR fillers results in enhanced FR classifications and mechanical properties

3. Excellent Lubrification

� Results in excellent smooth surfaces

� No die drol

Depending on the chosen TEGOMER®

additive. they can easily charged into the

main feeder or by direct injected into the

kneader

Seite | 10

Improvement of Processing Enables

Higher Out Put

Torsional moment

[A%]Extrusion head pressure

[bar]

40

50

60

70

80

without

additive Competitor

Product

Competitor

Product

TEGOMER®

V-Si 4042

(liquid)

TEGOMER®

V-Si 4042

(liquid)

1.0 % Additiv

2.0% Additiv

without

additiveTEGOMER®

FR 100

(solid)

TEGOMER®

FR 100

(solid)

TEGOMER grades for HFFR compounds lower the amperage use and the extruder

head pressure. They work as internal lubricant. give less abrasion and therefore

reduced maintenance costs.

Example: EVA Compound with 65 % Mg(OH)2

Seite | 11

Influence of TEGOMER® on the MFI in

HFFR/EVA Compounds

4.0

5.0

6.0

7.0

8.0

without

additive

Competitor

Product

TEGOMER®

V-Si 4042

(liquid)

5.0 6.5 6.5 7.0 7.0

MFI 190°C/10 kg [g/10 min]

TEGOMER®

FR 100

(solid)

6.8 7.0

TEGOMER® works as a

highly efficient dispersing

aid and internal lubricant.

not only as an external

lubricant as silicon oil.

Therefore. it enhances the

MFI of high filled HFFR

compounds and optimizes

the melt flow to receive

excellent cable surfaces. 1.0 % Additiv 2.0% Additiv

Example: EVA Compound with 65 % Mg(OH)2

Seite | 12

65% Mg(OH)2 untreated

without Additive65% Mg(OH)2

untreated

65% Mg(OH)2

amino silane treated

65% Mg(OH)2

vinyl silane treated

TEGOMER® V-Si 4042 for HFFR Compounds

Treated and Untreated Mg(OH)2 in EVA

2% TEGOMER® V-Si 4042

TEGOMER® V-Si 4042 improves machine parameters such as extrusion head pressure

and torsional moment significantly for a) untreated fillers and

b) even for silane treated grades

114108

103

67

53 5356

0

20

40

60

80

100

120

extrusion head pressure (bar)

torsional moment A%

92

Seite | 13

Influence of OMS Additives on the Melt

Viscosity of HFFR/EVA Compounds

65% Mg(OH)2untreated

65% Mg(OH)2amino silane treated

65% Mg(OH)2untreated

65% Mg(OH)2vinyl silane treated

+ 2% TEGOMER® V-Si 4042no Additive

TEGOMER® grades allow significant lowering of

the Mooney viscosity

TEGOMER® grades enable to use cheaper

untreated filler grades

TEGOPREN® 5885 can be used as well and might

create a higher gloss on the final cable surface

65% Mg(OH)2untreated

+ 2% TEGOPREN® 5885

0

10

20

30

40

50

60

70

80

1 2 3 4 5

Time [Min]

Mooney units [MU] 190 °C

Mo

on

ey u

nit

s [

MU

] 1

90

°C

Time [min]

10

80

70

60

50

40

30

20

1 2 3 4 5

Seite | 14

Standard Measurement Devices for

Flame Resistance

UL 94V CC

(Cone Calorimeter)

Source: Nabaltec/Germany

LOI

(Lowes Oxygen Index)

Seite | 15

Char Formation

65% MDH in EVA

65% MDH in EVA without Additive

65% MDH in EVA with TEGOPREN® 5885

No

AdditivTEGOMER

®

V-Si 4042

TEGOPREN®

5885

Char Formation depends on the selection of the right

organomodified siloxane

�TEGOMER® V-Si 4042 is preferred for compounding

�TEGOPREN® 5885 is very efficient for surface treatment

Seite | 16

Cone Calorimetry

EVA 19, 65 wt.-% MDH

Without

Additive

LOI: 38

+ 2% TEGOPREN®

5885 comp.

LOI: 45

+ 2 % TEGMER®

V-Si 4042 comp.

LOI 43

+ 1 % TEGOPREN®

5885 treat.

LOI: 42

Seite | 17

Heat Release Rate

EVA 19, 65 wt.-%

0

50

100

150

200

250

300

350

0

50

100

150

200

250

300

350

400

450

500

550

600

Time [s]

HR

R [

kW

/qm

]

MDH without Additive

MDH + 2% TEGOPREN® 5885 comp.

MDH + 2% TEGOMER® V-Si 4042 comp.

Seite | 18

Heat Release Rate

EVA 19, 65 wt.-%

0

50

100

150

200

250

300

350

0

50

100

150

200

250

300

350

400

450

500

550

600

Time [s]

HR

R [

kW

/qm

]

ATH without Additive

ATH + 2% TEGOPREN® 5885 comp.

ATH + 2% TEGOMER® V-Si 4042 comp.

Seite | 19

Rate of Smoke Released

EVA 19, 65 wt.-%

MDH + 2% TEGOMER® V-Si 4042 comp.

MDH without Additive

MDH + 2% TEGOPREN® 5885 comp.

0

1

2

3

4

5

6

0

50

10

0

15

0

20

0

25

0

30

0

35

0

40

0

45

0

50

0

55

0

60

0

Time [s]

RS

R [

m²/

s m

²]

Seite | 20

Rate of Smoke Released

EVA 19, 65 wt.-%

ATH without Additive

ATH + 2% TEGOPREN® 5885 comp.

ATH + 2% TEGOMER® V-Si 4042 comp.

0

1

2

3

4

5

6

0

50

10

0

15

0

20

0

25

0

30

0

35

0

40

0

45

0

50

0

55

0

60

0

Time [s]

RS

R [

m²/

s m

²]

Seite | 21

Highest Flame Retardant Classification

Due to Efficient Filler Dispersion

Compounds created by using

2% of TEGOMER® Grades

result in better flame

resistance and LOI

Flame 38 mm

Sample 126 mm

Distance

19 mm

BurnerCotton

Material Classification according UL 94 V (Vertical Burning Test) V-0 V-1 V-2

Combustion time for each specimen. 1. treatment ≤10s ≤30s ≤30s

Flaming and glowing combustion for each specimen (1. + 2. treatment) ≤30s ≤60s ≤60s

Total flaming combustion for all 5 specimens of any set ≤50s ≤250s ≤250s

Cotton ignited by flaming drips no no yes

Seite | 22

Flame Retardancy UL94

EVA 19, 59-65 wt.-% ATH

ATH

content

without

additive

2%

V-Si 4042

compoun-

ding

1%

V-Si 4042

treatment

2%

TP 6875

compoun-

ding

1%

TP 6875

treatment

2%

TP 5885

compoun-

ding

1%

TP 5885

treatment

0.5%

TP 5885

compoun-

ding

59% failed failed failed V-1 ? ? ? ?

61% failed V-0 V-0 V-0 V-0 V-0 V-0 V-0

63% V-1 V-0 V-0 V-0 V-0 V-0 V-0 V-0

65% V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0

? = not carried out so far

A loading of 65% ATH is needed to receive the V0 classification. By using

organomodified Siloxanes. as processing and dispersing additives. the

loading could be reduced down to 61%.

Seite | 23

Influence of OMS Additives on the

Dispersion of FR

The higher the loading with inorganic FR the more easy is

insufficient dispersion of the FR even visible at the exterior

roughness of the extruded material

The dispersion of FR in the inner bulk phase is influencing

mechanical properties

E-Modulus has to be balanced with elongation and an

average tensile strength is considered as minimum

requirement

� TEGOMER® V-Si 4042 can be used in the compounding

with up to 2% addition for MDH and ATH whereas

TEGOPREN® 5885 needs lower addition levels

� TEGOPREN® 5885 as well as TEGOPREN® 6875 are

suitable substances for surface treatment of MDH and

ATH whereas TEGOMER® V-Si 4042 is not suitable

65% ATH in EVA with

2% TEGOMER® V-Si 4042

65% ATH in EVA without additive

Seite | 24

� They act as internal lubricants and

dispersant to reduce abrasion and avoiding die drol

� Higher output by optimized melt rheology

� Less pressure built-up and amperage draw during

extrusion

� Less maintenance costs

� Better dispersion of fillers resulting in very good flame

resistant classification

� Smooth cable surfaces with excellent printability

Benefits of Organomodified Siloxanes in

HFFR Compounds

Seite | 25

Organomodified Siloxanes -

Outstanding Properties in Performance

TEGOMER®

TEGOPREN®

Silicone oil

masterbatches

Cable Compounding

MAA grafted

compatibilzer

Silanes

Throughput / Lubrification

Melt flow / MFI

Filler distribution

Cable Extrusion

Flame retardency classification

Surface smoothness

Migration

Printability

Low Oxygen Index (LOI)

Die drol

Gloss

Mech. properties

Filler loading

+ -O+

+ -O+

+ ++O

+ -O+

+ O+-

+ -O+

No NoNoYes

+ ++-

+ O+O

No YesNoNo

+ -OO

+ ++-

+ = good O = moderate - = bad