Huber Engineered Materials
SURFACE MODIFIED
ALUMINUM HYDROXIDE AND
MAGNESIUM HYDROXIDE FOR
POLYMER APPLICATIONS
HYMOD
VERTEX
ZEROGEN
®
®
®
HUBER ENGINEERED MATERIALS, A BUSINESS UNIT OF J. M. H
SPECIALIZES IN DESIGN, PRODUCTION AND MARKETING OF
ALUMINA TRIHYDRATE (ATH) AND MAGNESIUM HYDROXI
Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3
Surface modification background information . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4
Benefits of surface modified vs. untreated ATH
and MDH additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6
Benefits of using Huber’s surface modified grades
of ATH and MDH vs. addition of surface treatment
chemical during compounding (“in-situ” modification) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .8
Huber Engineered Materials’ surface modification capabilities . . . . . . . . . . . . . . . . . . . . . . . . . .10
0% Surface Treatment
0.25% Surface Treatment
0.5% Surface Treatment
Picture on the front page courtesy of Degussa Corporation: Dynasylan® MEMO
2
1.0% Surface Treatment
HUBER CORPORATION,
F A BROAD RANGE OF
IDE (MDH) PRODUCTS.
Huber Engineered Materials’ ATH and MDH product
lines include a wide choice of particle sizes, particle
distributions, morphologies and color characteristics,
as well as surface-modified grades utilizing a broad
selection of surface chemistries. These materials
are primarily used as flame retardant additives
to thermoplastics, thermosets and elastomers.
Surface treatment technology is one of Huber’s
core competencies.
Physical Property Comparison of Aluminum
Hydroxide (ATH) and Magnesium Hydroxide (MDH)
Property
Al(OH)3
Mg(OH)2
Powder
Powder
Hexagonal Platelet
Hexagonal Platelet
White
White
Specific Gravity g/cm33
2.42
2.36
pH Value
9-10
10-11
Hardness, Mohs
2.5 – 3.5
2.0 – 3.0
Refractive Index
1.57
1.58
Temperature of Decomposition
220 °C/428 °F
330 °C/626 °F
Heat of Decomposition, cal/g
280
328
Theoretical loss on ignition, %
34.6
31.0
Physical Form
Particle Morphology
Color
3
surface modification
background information
Most inorganic additives used in thermoset, thermoplastic and elastomer formulations have
hydrophilic surfaces and are therefore incompatible or poorly compatible with polymers. The
surface chemistry of ATH and MDH is characterized by the presence of large quantities of hydroxyl
groups and a percentage of free moisture (0.1-0.8 weight %). The surfaces of both materials are
highly hydrophilic. Incompatibility between the inorganic additive and polymer often leads to
incomplete dispersion of the additive in the formulation, and deterioration of physical properties,
including mechanical properties and flame retardancy. Surface modified grades of ATH and MDH
are used to overcome this problem.
Structure of Silanes
Surface modification involves deposition of a very thin
(molecular) layer of a certain chemical on the surface of
an inorganic additive in order to alter the additive’s
surface properties and make it more compatible with
the polymer.
There are three major categories of surface treatment
chemicals:
•N
•
No
onn R
Reeaacc tt ii vvee
– surfactants (anionic, cationic or non-ionic).
•R
•
Ree aacc tt ii vvee,, nno
onn cco
o uup
pll ii nngg
– fatty acids and their salts, alkyl or phenyl silanes.
•R
•
Ree aacc tt ii vvee C
Co
ouu p
pllii nngg
– vinyl-, amino-, sulfur- , epoxy-, methacryl- silanes.
R
REPRESENTS THE FUNCTIONAL GROUP THAT INTERACTS OR
REACTS WITH AN ORGANIC MATERIAL, SUCH AS SYNTHETIC RESIN.
•
•
•
•
•
R’
VINYL
EPOXY
AMINO
METHACRYL
MERCAPTO, ETC.
REPRESENTS THE HYDROLYZABLE FUNCTIONAL GROUP THAT
REACTS WITH AN ADDITIVE MATERIAL SUCH AS
•
•
4
METHOXY
ETHOXY
ATH
AND
MDH.
Interaction of Silanes with the
Surface of Inorganic Additives
In the case of a silane, the silicon-functional side of
the molecule undergoes hydrolysis on the inorganic
additive surface in the presence of surface hydroxyl
groups and adsorbed moisture. As a result of the
hydrolysis reaction, silanol groups Si-OH are formed.
Si-OH groups can form a hydrogen bond with the
surface of the additive and/or undergo condensation
reactions resulting in formation of siloxane oligomers.
Condensation reactions with surface hydroxyls are also
possible, leading to the grafting of siloxane oligomers
to the surface.
The organic-functional end of the silane molecule
determines how the surface modified inorganic material
interacts with a polymer. Non coupling silanes (alkyland phenyl-functional) improve wetting of the inorganic
surface with the resin and the quality of dispersion.
Coupling silanes (vinyl-, amino-, sulfur- , epoxy-,
methacryl- silanes) may form a chemical bond with
the polymer and significantly improve physical
properties of the composite.
Interaction of Surfactants
with the Surface of
Inorganic Materials
IN
THE CASE OF SURFACTANTS AND FATTY ACIDS , THE
HYDROPHILIC PART OF THE MOLECULE FORMS A BOND
(HYDROGEN
OR IONIC ) WITH THE SURFACE OF THE
INORGANIC ADDITIVE , WHILE THE HYDROPHOBIC PART
OF THE MOLECULE CHANGES THE SURFACE ENERGY OF
THE INORGANIC ADDITIVE TO MAKE IT MORE COMPATIBLE
WITH THE HYDROPHOBIC RESIN .
5
Brabender Torque, mg
Dynamic Thermal Stability. min
3600
9:36
8:24
3400
3200
Benefits of surface modified vs.
untreated ath and mdh additives
7:12
Rate of Heat Release, kW/m2
250.00
6:00
4:48
3:36
2:24
1:12
0:00
200.00
150.00
100.00
Micral 9400D
50.00
0.00
0.00
3000
2800
2600
2400
2200
2000
None
Hymod M9400SF
200.00
400.00
600.00
800.00
Low
Treatment
High
1000.00
Surface modification of ATH and MDH
can bring multiple benefits to the polymer
Time, seconds
applications, including:
Better Processability
10
1
0.1
9400SP Surface Modified ATH
5
10
15
Hymod M9400SF
Loading, phr
SURFACE MODIFICATION DRASTICALLY
OF ATH/SILICONE OIL MIXTURE.
20
3400
3200
3000
2800
2600
2400
2200
32.4
800
30.4
600
28.4
400
26.4
200
24.4
0
None 0
2000
25
34.4
1000
Tensile Strength, psi
Brabender Torque, mg
Viscosity, Pas
9400 Untreated ATH
0.01
0
Micral 9400D
36.4
3600
LOI, %
Improved Rheology
22.4
0.2
0.4 High
0.6
0.8
1
Low
Treatment Level, %
Treatment
OPTIMIZED SURFACE TREATMENT LEVEL BENEFITS PROCESSABILITY
( LOWER B RABENDER TORQUE ), WHILE AT THE SAME TIME
IMPROVES FR PERFORMANCE OF MDH FILLED POLYPROPYLENE.
DECREASES THE VISCOSITY
MICRAL® 9400 UNTREATED ATH AND HYMOD® M9400SP
VINYLSILANE TREATED ATH IN 50 CST PDMS
65%
OF
MDH
SURFACE TREATED WITH FATTY ACID IN
POLYPROPYLENE
0
J.M. HUBER CORPORATION MANUFACTURES MULTIPLE
SURFACE
MODIFIED
9400 Untreated
ATH PRODUCTS . THE SELECTION OF A
1
CHEMICAL PROPERTIES OF THE POLYMER SYSTEM. OUR
TECHNICAL STAFF IS READY TO ASSIST OUR CUSTOMERS
IN IDENTIFYING THE BEST SURFACE MODIFIED ATH AND
1
MDH FOR YOUR APPLICATION.
9400SP Surface Modified ATH
1000
Tensile Strength, psi
SPECIFIC SURFACE TREATMENT TYPE IS BASED ON THE
800
600
400
200
0
1
0
5
6
10
15
Loading, phr
20
25
0
0.2
0.4
0.6
0.8
Treatment Level, %
1
1.2
1.4
Rate of Heat Release, kW/m2
250.00
200.00
150.00
100.00
50.00
0.00
0.00
200.00
400.0
Tim
Improved Thermal Stability
200.00
150.00
100.00
50.00
0.00
0.00
200.00
400.00
600.00
800.00
1000.00
9:36
8:24
7:12
6:00
4:48
3:36
2:24
1:12
0:00
Micral 9400D
Time, seconds
SURFACE
MODIFICATION IMPROVES
FR
PERFORMANCE OF
EVA
FILLED WITH MAGNESIUM HYDROXIDE .
Brabender Torque, mg
BLUE LINE- 64% OF UNTREATED MDH IN EVA.
3600
ORANGE LINE - 64% OF MDH SURFACE MODIFIED WITH
VINYLSILANE IN EVA
3400
Hymod M9400SF
S URFACE MODIFIED ATH INCREASES D YNAMIC T HERMAL
STABILITY OF PVC FORMULATIONS. DYNAMIC THERMAL STABILITY
IS THE PROCESSING TIME BEFORE PVC DARKENS .
36.4
30 PHR MICRAL® 9400 UNTREATED
ATH
9400SF SILANE TREATED ATH IN PVC
34.4
3200
AND
HYMOD®
32.4
10
3000
Other Benefits of Surface
Modification
2800
30.4
LOI, %
250.00
Dynamic Thermal Stability. min
Rate of Heat Release, kW/m2
Better Flame Retardancy
9400 Untreated ATH
Viscosity, Pas
• Improved compatibility, easier dispersion
leading to higher loadings. 28.4
2600
1
26.4
• Uniform physical properties.
2400
• Better wet-out between resin and inorganic
additive.
24.4
2200
• Hydrophobicity, lower water absorption.
22.4
2000
0.1
None
Low
High
• Better
reinforcement due to coupling between inorganic
additive and polymer.
Hymod
M9400SF
Treatment
9400SP Surface Modified ATH
• Higher tensile and flexural strengths.
0.01
• Greater impact and scratch resistance.
0
5
10
15
Loading, phr
• Improved heat aging properties.
20
25
7
Benefits of using Huber’s surface modified
grades of ATH and MDH vs. addition
of surface treatment chemicals during
compounding (“in-situ” treatment).
600.00
800.00
1000.00
seconds
Some polymer processing companies elect to use untreated ATH and MDH materials in
applications where surface modified grades are desirable. They add surface treatment chemicals
(most often silane coupling agent) during compounding. These companies should consider the
3600
36.4
3400
34.4
3200
32.4
3000
I. Surface Treatment is More
2800
Uniform
2600
Huber’s surface modified products are engineered to
2400
achieve uniform surface treatment. Uniformity of the
2200 is very difficult to achieve by adding
surface treatment
surface treatment
2000 chemicals during the compounding
Low may lead
High to
process. Non-uniformNone
surface treatment
Treatment
an undesirable variation in composite performance.
30.4
28.4
LOI, %
Brabender Torque, mg
following benefits of using Huber’s surface modified grades of ATH and MDH:
II. Less Surface Treatment
Chemical is Used
26.4 “In situ” surface treatment requires the addition of
larger quantities of surface treatment chemical to
achieve desired results. This may lead to the presence
22.4 of unreacted chemical in the formulation resulting
in application problems.
24.4
Tensile Strength, psi
1000
800
600
400
E FFECT
STRENGTH OF
200
B LUE
0
0
0.2
0.4
0.6
0.8
Treatment Level, %
8
OF THE AMOUNT OF SILANE ON TENSILE
1
1.2
1.4
LINE
-
ATH
FILLED SILICONE RUBBER :
SURFACE MODIFIED
ATH
O RANGE LINE – SILANE ADDED “ IN - SITU ”.
140 PHR OF ATH IN PEROXIDE CURED
SILICONE RUBBER.
III. No By-Products Released
The reaction of silane coupling agents with the surface
of ATH or MDH or with free moisture generates large
amounts of volatile by-products, normally methanol or
ethanol (see Table below). These by-products may present
health risks for employees, in addition to possible safety
risks associated with detonation of alcohol vapors. The
presence of alcohol in a polymer formulation can cause
problems in the end-use application.
IV. Handling of silanes is a
challenge for manufacturing
Most silanes are hazardous chemicals, some of them
are flammable. Silanes are also moisture sensitive.
Silanes need to be stored in electrically grounded
containers, preferably under controlled temperature
conditions. By using Huber’s surface treated grades of
ATH and MDH you avoid dealing with these problems.
V. Other benefits
Amount of alcohol liberated
from some common silanes
Silane
• Fewer ingredients to handle
• Cleaner work environment (no liquid spills).
Amount of alcohol
liberated from
100 lbs of silane
1 Vinyltriethoxysilane
72.6 lbs of ethanol
2 Isobutyltriethoxysilane
62.7 lbs of ethanol
3 Gamma-aminopropyltriethoxysilane
62.4 lbs of ethanol
4 Phenyltrimethoxysilane
48.5 lbs of methanol
O UR SURFACE SCIENCE
LABORATORY
IS AVAILABLE TO ASSIST OUR EXISTING
AND POTENTIAL CUSTOMERS CURRENTLY
USING
“IN-SITU”
TREATMENTS , WITH
THE SELECTION OR DEVELOPMENT OF
NEW SURFACE TREATED PRODUCTS FOR
THEIR TARGET APPLICATIONS .
75 GRAMS OF GAMMA-AMINOPROPYLTRIETHOXYSILANE (AMEO)
GENERATES 46.8 GRAMS OF ETHANOL DURING HYDROLYSIS
9
Huber Engineered Materials’
Surface Modification Capabilities
Surface modification technology is one of the core competencies of Huber’s ATH/MDH business
unit. Our surface science laboratory, surface treatment pilot plant and two manufacturing facilities
are dedicated to serving customers requiring surface modified grades of ATH and MDH. These
facilities are located in Fairmount, GA and Kennesaw, GA. We achieve optimized product
modification conditions based on staged product development and manufacturing scale up.
At Huber, we continue to look for opportunities to develop new products and to improve the
quality and performance of our surface modified materials.
Our Surface Science laboratory has access to a broad
range of bench-scale and pilot-scale surface treatment
equipment, as well as various analytical instruments.
Bench-Scale Surface
Treatment Equipment
Analytical
Instruments
Pilot-Scale Surface
Treatment Equipment
Bench Scale Reactors
TGA Q-500
Littleford blenders (50 L, 100 L)
Henschel Mixers - 10L
DSC Q-100
Henschel mixer 75 L
1 hp High Speed Disperser
DMA
5 hp High Speed Disperser
Humidity Cabinets
LECO Carbon Analyzer
Micro-Sample Mill
Vacuum ovens
Cilas PSA (LLS)
Kemutec Centrifical Sifter
Mills
Sedigraph PSA
Kemutec Centrifical Mini Sifter
Surface Area BET
Rheometer AR-1000
Moisture balance
Brookfield Viscometer
10
Huber’s technical staff is eager to work with you to
identify the best surface-treated ATH and MDH for
your application. Our Fairmount Technical Center can
perform a wide variety of application testing (fire
retardancy, mechanical and electrical properties).
We also offer our customers the possibility of optimizing
existing surface modified products or development of
new surface modified products to satisfy their changing
requirements. We can:
1. Determine regulatory status of the new surface
treated product.
2. Develop surface treatment processes in the lab.
3. Prepare lab scale samples (< 1 gal).
4. Work with customers to optimize surface
treatment chemistry and treatment levels
and prepare lab scale samples.
5. Prepare pilot scale samples (approx. 20 gallons).
6. Optimize production scale surface treatment process.
The production of all our surface treated products
is backed with SQC/SPC methodology, along with
stringent QC/QA practices and Six Sigma process controls.
The Fairmount, GA production facility is ISO 9001
and ISO 9002 certified.
PILOT
AND LABORATORY SCALE SURFACE TREATMENT
EQUIPMENT AT
FAIRMOUNT TECHNICAL CENTER
11
For more information about Huber surface treated products, contact
the Huber Business Development Center at 1-866-JMHUBER.
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Huber Engineered Materials
J.M. Huber Corporation
1000 Parkwood Circle, Suite 1000
Atlanta, GA 30339
Phone – 1-866-JM HUBER
Main – 678-247-7300
Email: [email protected]
TTEE C
CH
HN
NO
O LLO
OG
G YY C
C EE N
NTTEERR
Huber Engineered Materials
J.M. Huber Corporation
251 Gordon Street
Fairmount, GA 30139
Phone – 706-337-3243
Fax – 706-337-3384
www.hubermaterials.com
THERE ARE NO IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE.
Refer to Huber's Standard Conditions of Sale for the only express warranties applicable to the Huber products. Products
incorporating Huber products are not warranted by Huber. In no event is Huber liable for consequential damages.
Hydrad®, Micral®, Hymod®, Onyx Elite®, PATH® are registered trademarks of J.M. Huber Corporation for alumina trihydrate.
Zerogen® is a registered trademark of J.M. Huber Corporation for magnesium hydroxide.
Vertex® is a registered trademark of J.M. Huber Corporation for magnesium hydroxide.
© 2006 J.M. Huber Corporation ATH / SSbrochure / NA / REVI August 2006