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Selecting Additives for Rubber Compounding

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4 views20 pages

Selecting Additives for Rubber Compounding

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mr
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© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

5/10/24, 11:22 AM Selecting Performance Additives for Rubber Compounding > RheTech

Selecting Performance Additives For


Rubber Compounding
March 5, 2020

Understanding And Selecting Performance


Additives For Rubber Compounding
By Mark Stewart, Sr. Technical Service Representative, HEXPOL Compounding

Abstract: This white paper addresses when and how to use performance additives. When
properly selected, performance additives bring value and clear benefits to the application.
They address manufacturing and process concerns to help maintain quality and consistency
during compounding.

The number of available additive options can be overwhelming to compounders and plant
chemists. Therefore, a systematic approach to performance additive selection should used
to define objectives clearly, such as: better throughput, precise control of critical
ingredients, lower costs with shortened mixing cycles, timely and complete dispersion,
worker safety, and color control, to name a few.

Reasons for using performance additives, proper selection of additives to meet application
objectives, different performance additive types, and manufacturing and cost benefits are
addressed in this white paper.

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Introduction
Use powders anytime they satisfy specifications and application requirements when
compounding and mixing rubber. Powders provide the least expensive approach to rubber
compounding. Additives are not needed when they don’t bring value or provide clear
benefits.

However, as this white paper will illustrate, the least expensive raw material doesn’t always
translate to the lowest cost compound. Consider a diamond mill configuration in a
compounding facility with a limited period of time to get cures dispersed on a two-roll mill
without a second pass. Additives provide the solution via mill acceleration with dispersions.
Other examples of beneficial uses of performance additives include reducing manufacturing
time, improving worker environment, and providing a safe means of handling difficult raw
materials.

But how do compounders and plant chemists find the right performance additives for their
applications? With so many options, the choices can be overwhelming. To start, desired
outcomes must be carefully defined. What is most important for a particular application? A
systematic approach is necessary that defines objectives clearly, such as: better throughput
and/or precise control of critical ingredients, lower costs with shortened mixing cycles,
timely and complete dispersion, minimized airborne dust, ease of handling and
incorporation, worker safety, and/or color control.

At what point do performance additives enter the compound mixing equation? In some
cases, such as evaluating a new formula, the goal is to identify possible issues and consider
performance additives to address those issues. However, until those potential issues are
validated on the mixing line, powders may be used in the formulation, unless clear-cut
safety concerns are identified.

Most additive scenarios occur when there is an existing process that needs improvement.
Plant managers and supervisors, as well as operators on the mixing line, can usually
identify issues that prevent operations from functioning and performing as desired. What
issues hinder the use of rubber or processing rubber as quickly as desired? The question is
what materials in the formulation should be evaluated?

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While reviewing a formula, plant chemists may find, for example, that a particular
ingredient doesn’t disperse, so a dispersion additive is needed. Does it need to be in pellet or
slab form? Does it need to be liquid? If it is a liquid, will a dry powder work better? Is it a
powder but it agglomerates badly so it needs separated? These are examples of identifying
beneficial uses of performance additives.

Finding the best additive solution can be difficult. This white paper will help compounders
understand and select prepared rubber chemicals or pre-dispersions of rubber chemicals
and colorants for their applications.

Reasons For Using Performance Additives


Designers and plant chemists sometimes have limited experience with rubber and often rely
on the analytical and resource capabilities of polymer compound service providers. They
may need assistance making selections for their applications. It’s true that performance
additives shouldn’t be used unless they bring value, but nearly 78% of all formulations
require some sort of additive. A typical formulation starts with a base rubber polymer, but
may have 10 to 20 additional ingredients that influence each other, as well as the end
product (See Figure 1).

Plant chemists may not know what’s available for mixing operations without outside
assistance. A compounding service provider’s chemists and technicians have to ask the
right questions about the application to make the correct assessment of the issue(s) to be
solved.

As important as it is for compounding service chemists to ask questions, it is equally critical


for the plant chemists and operators to share information about their objectives, processes,
and equipment. For example:

Describe the toughest problems, difficulties, and red flags they face on the factory
floor
Clearly define performance improvement/efficiency goals
Identify the time-consuming steps in the current work flow

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Figure 1

It is incumbent upon compound service providers to spend time on the factory floor with
plant chemists and mixing line operators to understand their goals and concerns to help
them find and implement the appropriate solutions. A give and take process of answering
questions and sharing information is essential. Multiple topics at the mixing plant should
be addressed, including:

Frustrations: Concerns about product quality, development cycle time, cost, and
environmental issues.

Formulations: Requirements specific to a final product’s critical characteristics aren’t


always clear, whether the product is tires, conveyor belts, hoses, molded goods, electrical
products (wire & cable) or consumer goods

Functional Components: There are always questions about and a need to understand raw
materials and their formulations. Raw materials include base polymers, fillers, vulcanizing
agents, process aids, plasticizers, lubricants, curatives, accelerators and activators,
protectants, colorants, blowing agents, and bonding agents (See Material Component
Overview on page 7).

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Forms of Components: Different form types, such as solids (e.g., slabs, bars, beads, and
pellets), liquids, or pastes impact handling, mixing efficiency, environmental issues.

Formulations: The type and size of mixing equipment, mixing processes, and capacity
utilization all present different processing issues to be considered.

Fabrication: Different fabrication methods, such as extrusion, injection molding, building


and curing affect formulation requirements and performance additive selection.

Financial Considerations: Performance additives cost more than powders, but improved
processing, shorter mixing cycles, and increased throughput more than offset initial cost
differences.

Performance improvements, process efficiency goals, and total cycle cost reductions are
what compounding service providers identify, evaluate, and strive to implement for their
mixing customers. The price of performance additives is not going to be less expensive than
powders (though only a small percentage of a formulation’s cost), but process
improvements and increased throughput contribute to lower total cycle costs as illustrated
in Figure 2 below. That’s a major reason why plant chemists should constantly ask these
types of questions when working with their compounding services provider. They should
expect technical and application leadership.

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Figure 2: “Using performance additives reduces overall finished compound cost while
improving quality and consistency. Improved efficiency leads toincreased capacity.”

Material Component Overview


Rubber Polymers – There are numerous grades of base polymers that vary in properties and
cost. Select the right polymer for your application because rubber does not have universal,
one-size-fits-all design criteria.

Fillers – Are available in several types: reinforcing, such as carbon black, semi-reinforcing,
such as ______________NEED FROM MARK, and non-reinforcing, such as calcium
carbonate. They help provide durability and performance in rubber compounds.

Plasticizers – They improve the rubber’s flow during processing, enhance filler dispersion,
and reduce compound viscosity.

Tackifiers – Provide short- and long-term tack in the compound that causes the two layers
to stick together with mild pressure. Tacky compounds don’t always stick to other surfaces.

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Process Aids – As the name implies, these chemicals improve the compound’s
processability.

Internal Lubricants – Are mixed into the compound to keep the compound from sticking to
process equipment and to lower heat build up.

Protectants – Includes antioxidants that slow deterioration caused by contact with oxygen,
antiozonants that slow deterioration caused by contact with ozone, and waxes, as well as
metal deactivators and flame-retardants.

Accelerators – Hasten the chemical reaction and optimize the cross-linking reaction to
speed up curing.

Activators – Strengthen accelerator performance and activate the vulcanization process.

Curatives – Sulfur, sulfur donors and other chemicals that cause cross-linking to occur.

Colorants – Are dispersions that eliminate cross-contamination of dry pigments, enhance


color consistency across batch lots, reduce costs and increase product quality.

Blowing Agents – Produce gas by chemical or thermal action when added to a rubber
compound in the manufacture of cell or sponge products.

Bonding Agents – They help hold dissimilar materials together in the finished rubber
article.

Vulcanizing Agents – These agents provide the chemical process for converting rubber or
related polymers into a more durable rubber-elastic material end product.

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An Overview Of Performance Additive Selection


Though there are virtually thousands of possibilities for using performance additives with
formulations, there are six primary manufacturing concerns that account for the majority
of performance additive applications. The suggested solutions provided here are addressed
in detail in the Power of Performance Additives section later in this white paper.

Manufacturing Concerns:

Scrap too high due to inconsistent weighing: Consider using oil treated, pre-mixed
powders, which are cleaner to handle and easier to weigh, to improve process and product
uniformity. They are delivered to the compounding plant surface wetted for faster mixing,
and multi-ingredient for reduced weighing, as well as the correct critical ratio of powders.

Too many ingredients to weigh for each batch: There are pre-weighed and packaged multi-
component powder blends that are heat-sealed in a low-melt batch inclusion bag. They are
customized to customer formulation and specialized weight, reducing labor and increasing
formulation accuracy.

Health, safety and environmental concerns: Leading compounding services providers


supply single- and multiple-component dispersions in clean, easy to handle solid forms –
such as slabs, strips, pellets, and cubes – with rapid incorporation during mixing.

Mill cure addition: Consider single- and multiple- component dispersions that are flexible
for custom requirements, and/or additives that feature encapsulation technology designed
for rapid incorporation.

Undispersed powder in batches: Identify the powder and substitute it with a dispersion of
that ingredient.

Cycle times are too long: Consider single- and multiple- component dispersions to replace
powders or additives that feature encapsulation technology designed for rapid
incorporation. These dispersions are flexible for custom requirements.

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Performance additives properly selected to address manufacturing and process concerns,


such as those listed above, help to maintain quality and consistency during compounding.
They are often critical to successful, efficient, and profitable compound manufacturing
because they:

Ensure timely and complete dispersion of active ingredients into the compound
Shorten mixing cycles, increasing machine output and reducing energy use
Minimize airborne dust in transport, on the factory floor, and on mill mixing lines
Simplify handling of difficult dry powders and raw materials
Provide a safer environment and reduced exposure for workers
Improve and extend compound shelf life

Financial considerations and cost reduction opportunities for using performance additives
include:

Reduced labor requirements: Less measuring of materials and clean up


Reduced mixing time: Rapid incorporation of materials
Reduced mixing cost through alternative procedures: Pre-manufacturing with
premixed ingredients
Reduced in-process losses: Oil-treated and polymer-based materials are easier to
handle and weigh
Improved product and process uniformity : Pre-weighed materials ensure the
consistency of every batch

Performance additives also contribute to the success of customized formulations that


require only small amounts – less than 100 pounds – of additives for __________ or
_________. There is a true need for performance additives when developing prototype
compounds.

Driving Forces For Using Performance Additives


The foundation of and driving forces for the use of performance additives are largely based
on four factors: dispersive vs. distributive mixing; powders vs. chemical dispersions;
prepared rubber chemical forms; and the importance of compatibility.

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Dispersive vs. Distributive Mixing –The first question to answer is why it is important to
have dispersion rather than distributive mixing (See Figure 3). D ispersive mixing ensures
that particles of a substance are scattered throughout the mix – reducing the size of a
cohesive minor component, the agglomerate – to determine the interaggregate separation
and filler network characteristics. Dispersive mixing is ideal for complex, difficult to mix
compounds that require a long mixing time. Proper techniques are necessary to ensure that
agglomerates remain separated.

With distributive mixing, proper rheology is critical and involves spreading the minor
component throughout the matrix to form a homogenous blend. High viscosity increases
incorporation time or leads to non-uniform distribution. The closer the rheology of the
varying compound components, the better the resulting final mix.

Imagine a tensile bar with a break at an undispersed accelerator material, which can over
cure and burn. Ideally, mixing strives for perfect dispersion. Without a performance
additive, multiple mixing passes may be necessary, but is the additional cost worth it? The
goal of these processing scenarios it to determine “how much is good enough and does it
work for the customer?” The goal is always to mix faster and more efficiently. This is
accomplished by using an additive that reduces the time it takes for proper dispersion.

Figure 3: The top left hand diagram Illustrates agglomerates in the mix because of a lack of
dispersion and distribution. The compound is riddled with chunks. The right hand box

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illustrates even distribution, but there are still too many agglomerates because of bad
dispersion. The left hand bottom box has good dispersion, but bad distribution. Perfect
dispersion and distribution is shown in the lower right hand box.

Powders vs. Chemical Dispersions – Figure 4 below does a good job of showing some of the
efficiencies of chemical dispersions. It illustrates possible inefficiencies of a dry powder
cure system on a two-roll mill. It is necessary to sweep up the powder and return it to the
rolling nip until it incorporates. Incorporation time is two minutes, and requires two pan
sweeps. Introducing a dispersion additive into the formulation significantly reduces the
incorporation time.

Figure 4: Chemical dispersion benefits include rapid incorporation, no caking on rolls or


powder dropping to the mill pan. M ixing times can be reduced dramatically.

Prepared Rubber Chemical Forms –Different form types, such as solids (e.g., slabs, bars,
beads, and pellets), liquids, or pastes impact handling, mixing efficiency, environmental
issues. These forms are addressed in detail in the Power of Performance Additives section of
this white paper.

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Importance of Compatibility – When using performance additives, compatibility with the


base compound is extremely important. As noted, the range of possible additive solutions
requires a thorough knowledge of the ramifications – positive and negative – for selecting
an additive. Compounders prefer and use different binders. Some have a nitrile compound,
so they select a nitrile binder. O thers use EPDM for their application, so they select EPDM.
SBR used to be the general binder for just about everything because of its low cost, but with
more specialty polymers, that is no longer the case.

Power Of Performance Additives


Solutions for these driving forces can be found in proprietary performance additives,
productivity enhancing pre-dispersed chemicals, master-batch products, and color
concentrates. An initial review of the available additives and their forms follows.

Pre-weighed Materials. Critical compound components, such as the cure system, are often
pre-weighed and provided by a third-party supplier. Low melt point bags are used and the
unit is added directly into the internal mixer.

When the multi-components are pre-blended on a large scale, improved uniformity can be
expected. During the blending operation, oil may be added to reduce dust loss when the bag
is broken in a mixer; pre-wet powders will incorporate faster.

Benefits include:

Improved product uniformity and process control


An “environmentally friendly ” package
Direct labor reduction
Reduced work, reduced downgrading, or reduced scrap

Dust-suppressed powders. Commonly treated by wetting with an oil or plasticizer, dust-


suppressed powders reduce dust. Fluid selection should be governed by the intended
application. A compatible fluid is required to achieve a reasonable incorporation time during
mixing. Incompatible fluids may bleed and cause fabrication problems and an unacceptable
final product. Regulatory considerations are also important if the final product is a medical
device, FDA regulated or a NSF governed product. Complete powder treatment is needed for
effective dust suppression. Over-treatment can lead to re-massing and handling problems.

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Commonly, fluid addition levels range from 4% to 20%. Because fluid application is
performed in low to medium intensity mixers, the particle size and agglomeration of the
original powder critically affects dispersion quality.

Dust suppression reduces direct material contact, inhalation hazards and in-process
material loss to dust collectors. Plant effluent streams, such as packaging residue and
contaminated clothing, are also reduced by treated powders.

Since fluid treatment may be performed in powder mixing equipment, an opportunity to


manufacture powder blends is present. Critical compound components, such as cure
systems, flame retardant systems, and multi-pigment colorants, are often prepared as pre-
blends. The main constraint for multi-component blends is chemically compatible, non-
reactive components. These pre-blends are often customer specified, proprietary
compositions.

Pre-blends reduce the number of weighings by compounders. Therefore, labor reduction


may be possible in large plants. Large scale powder blending can improve blend
composition uniformity. This often yields improved process and product uniformity.
Improved uniformity normally translates into improved quality and reduced manufacturing
costs.

Encapsulations. The composition of the encapsulating material is dictated by compatibility


and regulator constraints. Since these products are mixed in low to medium intensity
equipment, the particle size and agglomeration of the basic powder component(s) is
important.

Polymer encapsulated powder products are completely dust-free and do not cling to
packaging or handling equipment. Thus, in-process losses are substantially reduced and the
product form is “environmentally friendly.” Re-massing is eliminated. Additionally, they
have an affinity for compounds, not mixing equipment surfaces. Plate-out on the surfaces
of mixing equipment is eliminated and mixing efficiency is maintained.

Properly handled, mixing times can be dramatically reduced and mill pan or internal mixer
throat sweeps can be eliminated (See Figure 5). These products have the appearance of
finely ground rubber and their small particle size facilitates distributive mixing. The rapid
incorporation of polymer-encapsulated powders has facilitated changes in mixing
procedures and resultant cost savings. Introducing cure components late in a single pass
mix can eliminate two-pass mixing requirements. If the cure system has a very short scorch
time, the compound may require some cooling before the curative(s) are added. This may be

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achieved on the drop mill below the internal mixer. Compared with dry powders,
incorporation times on a 2-roll mill can be reduced by over 50% with polymer encapsulated
powder substitution.

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Figure 5: Diamond Mill Configuration

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Absorbed “ Liquids” (Dry Liquid Powders) . A low melting solid or viscous liquid is difficult
to handle and mix. Often, the material must be heated to handle, creating a safety hazard.
Adding liquids during mixing lubricates compounds and reduces shear input. However, they
must be added slowly to maintain effective mixing. Such materials are often absorbed on
high surface area carriers. The final product handles like an “oiled” powder. Carrier
selection may be tailored to the final application. Products utilizing fumed silicas or
diatomaceous earth can achieve 60 to 75% activity. Unfortunately, these carriers are prone
to moisture pick up. Unless the carriers are dried prior to use, moisture is expected. For
moisture sensitive materials or applications, calcined clays may be used. They are not as
prone to moisture pick up. Due to their lower surface area, final products are typically 30%
to 40% active. Some of the common material handled in this fashion are petroleum oils,
ester plasticizers, low softening point resins (pine tar, rosin, coumarone-indene, phenolic,
etc.), waxes, low molecular weight liquid elastomers, adhesion promoters, silane coupling
agents, co-agents and peptizers.

Benefits include:

Improved handling
More accurate weighing and addition
Reduced packaging losses
Improved mixing

Partitioned “ Solids.” Lower melt point solids, such as tackifing resins, are often supplied
in drums. Due to their low melt point, the material is one large mass. To handle these
materials, they must be broken or crushed into small particles that can be weighed and
mixed. Unless the particles are partitioned, they will re-mass. Partitioning agents are
usually clay, precipitated silica or diatomaceous earth. The prime benefit of this form is
improved handling which translates into reduced labor costs and decreased health and
safety issues.

Polymer based Dispersions. The key factors that determine dispersion quality are the raw
material quality, the dispersion formulation, processing equipment and mixing procedure.
A polymer based binder system (continuous phase) should be of sufficient viscosity at
processing temperature to ensure adequate shear input to attain good deagglomeration and
uniform dispersion. The pre-dispersion must be soft enough at processing temperatures to
attain good distributive mixing in the final compound. The binder system should also be
non-reactive polymer that is compatible with the final compound and its application. For
these reasons, dispersions based on NR, SBR, NBR, EPR, EPD M, EPD M/EVA, CPE, CR, PVC,
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various other thermoplastic polymers, or customer specified polymer grade and/or source
may be required. Single component dispersions are the most common; however, multi-
component dispersions are produced to customer specification. These dispersions are
limited to non-reactive compositions.

Benefits obtained when powders are replaced with polymer-based dispersions include:

Improved material handling


Reduced mixing time (Mixing is distributive rather than dispersive.)
Improved product & process uniformity when a multi-component dispersion is used
Reduced in-process material shrinkage
Lower scrap and/or downgraded product
Improved environmental conditions (Both direct contact & indirect contact are
reduced.)

Paste Dispersions. Chemical or color paste dispersions are often used in very low viscosity
compounds to achieve good dispersion and distributive mixing. The same constraints are
present with paste dispersions as were noted for all previous systems. Fluid selection and
multi-component limitations are important. Paste dispersions can range from fairly low
viscosity products that are pumped and metered to products so viscous; they are extruded as
bar forms.

Dispersion quality should be specified to ensure adequate quality for the final application.
Generally, paste dispersion cost is directly related to the quality of dispersion specified.
Paste dispersion quality or deagglomeration may be measured by the Hegman NS Grind test
(ASTM D -1210). This simple test measures the maximum residual particle size and
expresses it as a number between 0 (100 microns) to 8 (0 microns).

Benefits include:

Improved dispersion and faster distribution in low viscosity compounds


Improved uniformity with multi-component paste dispersions
Reduced re-work , downgrading and scrap

Coloring Rubber Compounds

Rubber technologists spend years learning how to compound and develop excellent
compound properties, yet few truly understand the importance of color selection and
dispersion to overall compound properties. Many do not understand the science of color,

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which is a topic for another white paper. The critical aspects of color perception for
consideration here are source, object, and observer. The source refers to the light source,
which defines color and dramatically affects how a color is perceived. When considering the
object, the surface type of the final part (a glossy, matte, or dull surface) affects color. The
final aspect, the observer, may be a human or a machine.

Color typically involves either dyes or pigments. Dyes are soluble materials that are
expensive, used at very low loadings, and ‘bleed’ or migrate out of rubber compounds.
Pigments are insoluble discreet particles used to color materials. Because of the migration
issues with dyes, pigments are used almost exclusively in rubber compounding applications.

Pigment Selection

The best time to select a pigment system is during the early phase of compound
development. Unfortunately color pigmentation is often an afterthought. Selecting the best
pigment(s) to meet specific application requirements is critical to choosing the most cost
effective and best performance colorants to provide an ideal balance of dispersion and
compatibility for the application. Pigment selection requires a thorough knowledge of the
final application requirements. Questions to answer include:

What is the desired color and how critical is the match?


What U.V. requirements exist?
Is it an outdoor or indoor application?
What processing temperatures will be used during the product’s manufacture, and
for how long will it be exposed to that temperature?
Is this a food contact application?
Is it required to be ‘heavy metal free’?
What is the expected life of this product – 1 day ? 20 years?
What are the cost constraints?

Color Delivery Systems

Once the pigments have been selected, the next crucial choice is the delivery system to
introduce the colorant into the compound. Dry colors, solid dispersions, and paste
dispersions are the most common types. Careful consideration of the delivery system is
critical to obtaining the lowest total manufacturing cost. This cost not only contains the raw
material cost, but also weigh up time, processing resources and scrap costs. Although dry

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color has a low initial raw material cost, the degree of difficulty in dispersing needed to
obtain the maximum pigment strength often requires a color concentrate. Color master
batches eliminate this and other issues found with dry colors. Several forms are available,
including slab, cube, pellet and paste.

Conclusion
Powders provide the least expensive approach to rubber compounding. Performance
additives are not needed when they don’t bring value or provide clear benefits. However, as
this white paper illustrated, the least expensive raw material doesn’t always translate to the
lowest cost compound. Examples of beneficial uses of performance additives include
reducing manufacturing time, improving worker environment, and providing a safe means
of handling difficult raw materials.

Objectives to be achieved when using additives include cleanliness, dispersion, color


control, ease of handling and worker safety, ease of incorporation, and precise control of
critical ingredients. To meet these objectives there are multiple performance additive types
to be considered and evaluated for each application, including pre-weighed materials, dust-
suppressed powders, encapsulations, absorbed liquids, partitioned solids, polymer-based
dispersions, paste dispersions, and color dispersions.

The cost reduction and manufacturing benefits of using performance additives include
reduced labor, mixing time, and in-process losses; less scrap, improved throughput,
improved product and process uniformity.

CONTACT OUR EXPERTS TO LEARN MORE

Sorry, there is no expert for this article.

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© 2020 HEXPOL AB. All rights reserved.

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