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FOR METALWORKING
Wisura Introduces Theory of How Fluids Work
BY RICHARD BEERCHECK
18
C onventional theories about
metalworking fluids state
that they react chemically with
Out with the Old
Schulz agrees with one
aspect of conventional
structures of various met-
als used in metalworking.
Using secondary ion mass
theories on metalwork- spectroscopy and second-
the surfaces of metal work- ing fluids: Additives must ary neutral particle-mass
be interacting with the spectroscopy, they found
pieces during the short time that workpiece in some way to different types of molecules
the two are in contact. These make it more amenable to covering surfaces of differ-
the metalworking process. ent metals. Iron surfaces
reactions supposedly form metal Without fluid, metalwork- are typically covered with
chlorinate, metal sulfide or metal ing tools generally wear hydroxyl groups, Schulz
out faster, the finish on said, while carbon steel
phosphor layers that are more
workpiece surfaces ends up is covered with a layer of
easily removed by the machine rougher and the likelihood hydroxides and oxides.
of adhesion between tool Oxides either cover the
tool.
and workpiece increases. entire area or create island-
Researchers at a German [S]ome type of reaction shaped patches. Stainless
supplier of metalworking fluids is essential to ensure long steels generally are covered
tool life and to produce an by chrome-oxides and
challenged that model recently, optimum surface finish, nickel-oxides, with the ratio
contending that, in most met- he said. between the two dependent
According to Schulz, on the specific alloy. And
alworking operations, the fluid research supporting the aluminum is covered by
and part are not in contact long conventional theories has a tenacious oxide layer.
basic flaws. One diffi- Thus, steel, stainless steel
enough for the complex reac- culty with commonly held and aluminum have quite
tions necessary to form these theories about metalwork- different surfaces and,
ing operations, he said, therefore, react differently
layers. In a January presenta- is that most published with additives.
tion at the OilDoc conference literature describes tests in Additives interact with
which the additives have a oxides, hydroxides or metal
in Rosenheim, Germany, Wisura lot of time, often hours, to ions, said Schulz. Gener-
GmbH Research and Develop-
Photo Neha Bhargava/Dreamstime; Illustration by Ricardo Lianez
AIR
www.axelch.com info@axelch.com
Since that is too little time for full- atom of a nonionic additive to bond
blown chemical reactions, conven- with a hydroxide group on the metal
tional theories describing the interac- surface, forming a so-called hydrogen
tions of metalworking fluids must bridge. Under the second, an ionic
be invalid, and a new one is needed, additive replaces the hydroxide group
Schulz said. The current model is on the surface. The third mechanism
based predominantly on the forma- has a nonionic additive adsorbing
tion of reaction layers on the metal onto to the metal atoms of an oxide
surface, and surfaces of different group.
an additive molecule have to interact metals are assumed to be chemically The first and second mechanisms
with the metal surface? Average ma- homogeneous, consisting primarily act on the same molecule group
chining time depends on the process. of oxide layers. In contrast, the new and, therefore, compete with each
For instance, broaching machines model minimizes the effects of reac- other for sites. If the metal surface
work at speeds from six to 30 meters tions between additives and metal contains both hydroxide and ox-
per minute, turning machines at 100 surfaces and relies mainly on the ide groups, reactions vary between
High Purity +
Premium Performance
Synthetic Ester Basestocks for:
Metalworking Fluids
Chain Lubricants
Greases
Compressor Fluids
H1 Food Machinery Lubricants
H H (+) (-)
(+) Fe
Functional group of
C O nonionic additive
O O O
C C
Iron hydroxide Functional group of Iron hydroxide Functional group of Iron oxide
nonionic additive ionic additive C
Source: Wisura
Mechanism 1 and 3 or Mechanism 2 shown to stabilize the micro-cracks in rates on stainless steel except for the
and 3. In either case, a synergistic ef- metallic materials, preventing them complex esters. A possible explana-
fect should be observed, Schulz said. from rewelding, thereby producing tion for this finding is that the elec-
These findings show that classical smaller chips. tron density and the higher viscosity
theories of chemical reaction have All metalworking processes, includ- of the molecules aid adsorption,
only limited application to metal- ing forming, generate fresh metal Schulz explained. Saturated fatty acid
working processes, Schulz con- surfaces, Schulz continued. If these esters showed the lowest adsorption
cluded. The dominant interaction surfaces are not covered immediately because their molecules have fewer
for metalworking fluids is adsorption by additives, the tool and part can binding sites.
of the additives to the metal surface. weld together. This effect has been On carbon steel, complex esters
Therefore, cleavage and recombina- observed most often with stainless showed better adsorption because
tion of molecules are not critical for steel, aluminum and titanium ma- their molecules have more binding
metalworking operations. terials covered by pure oxide layers sites. Schulz added that the influ-
Wisuras research shows that long- and less frequently with carbon steel ence of viscosity cannot be totally
chain chlorine- or sulfur-containing or yellow metals. Adhesion occurs excluded although higher viscosity
paraffins do not react with the metal because the freshly machined metal is fluids do not always show higher
at the surface temperatures produced in a highly reactive state and readily adsorption.
and in the time interval common for forms new chemical bonds. Adhe- To provide more insight into the
metalworking operations. Rather, sion can be avoided only if additives impact of esters, they were combined
said Schulz, the reaction depends on quickly adsorb onto the new surface. with other additives: a polysulfide,
the molecular structure of the metal which prefers to bond with oxide
surface, the type of additive and Testing the Theory groups and to a lesser degree create
whether the additive finds an attach- To test the validity of their new hydrogen bridge bonds, and over-
ment point. theory, Wisura researchers formu- based sulfonates, which prefer to
Schulz explained that other re- lated fluids consisting of triglycerides, form ionic bonds.
search has shown that surface-active fatty acid esters and complex esters In theory, the polysulfide should
additives greatly reduce the energy in a mixture with 60 percent naph- bind preferentially with oxide groups
required for the forming process. This thenic base oil. Ester-based addi- on metal surfaces, thereby inhibiting
is further evidence that adsorption is tives were used because they do not the adsorption of esters. Surprising-
the dominant interaction. Specifi- react chemically with other additives ly, Schulz said, adsorption values
cally, he said, surface-active addi- or metal surfaces and should work showed the opposite effect, rising
tives increase the flow rates of metals according to both the old and new with the addition of only 2 percent
and reduce their fatigue strength. In theories, said Schulz. polysulfide. This means that esters
cutting operations, the additives were The results showed low adsorption and polysulfides do not compete for
We distribute
that esters work mainly by Recognizing the presence
creating hydrogen bridge of hydroxides and oxides
bonds and not by adsorp-
tion to the oxide groups.
Schulz said that higher
on the surface leads to
good predictions about the
behavior of additives or
for you
values on stainless steel are
due to the adsorptive effect
their mixtures. Synergistic
and antagonistic effects can
now even
of the polysulfide because be explained by the differ- more products
the additive cannot react ent affinity of additives to
chemically with the high-
grade steel surface.
certain surface structures.
Generally, oxide sur-
Group I / II / III,
To corroborate the new
theory, mixtures that more
faces on stainless steel,
aluminum, and titanium
PAO, PIB, esters
closely match commercial-
ly available coolants were
are unable to react with
ionic additives; rather,
specialties
examined. The highest they interact only with
adsorption values were nonionic additives. The
produced by triglycerides bond between oxygen and
on carbon steel. The results iron, chromium or nickel is
show that the performance very stable and cannot be
of esters depends on how severed by metalworking
their oxygen atoms bond additives. They can only
with hydrogen atoms of adsorb onto the surface.
the hydroxides, Schulz A surface more or less
said. The same effect was covered with hydroxides
observed on stainless steel. can react with both non-
In the test matrix, the ionic and ionic additives,
active polysulfide was re- Schulz said. Reactions
placed by a different active between hydroxides and
polysulfide and in a third ionic additives replace the
trial by an inactive polysul- hydroxyl-group with the at-
fide. Researchers kept sul- tacking ion. Reactions with
fur levels steady in all three nonionic additives create
cases. The results show that hydrogen bridge bonds.
changing the polysulfide Finally, Schulz said,
had no significant influence More work is required
on the results. This means to describe the activity of
that the rate of adsorption other additives such as
depends not on the activity antiwear compounds. It is
of the polysulfide, but only to be hoped this investiga-
on the sulfur content itself. tion can be helped along by
transferring the knowledge www.mogoil.com | info@mogoil.com
Moving Forward compiled here about how Tel. +49 30 240 88 29-0 | Fax +49 30 240 88 29-29
Schulz concluded by say- different additives interact MOGoil GmbH | Rother Strae 17 | 10245 Berlin | Germany
ing, The results of these with various surfaces. o
LUBESNGREASES EUROPE-MIDDLE EAST-AFRICA MAY 2013 23
BY BORIS KAMCHEV
BUCKLING DOWN
IN THE BALKANS
REGIONS LUBE COMPANIES COPE WITH TOUGH TIMES
The Balkans is known for its tough terrain and tough political history. Fortu-
nately, this area of Southeast Europe is currently enjoying a period of relative
calm. But things are still difficult for its lubricant industry, according to an
official from one supplier in the sub-region.
Speaking in March at the Argus European Base Oils Conference in Istanbul,
Mirjana Kolb, of Serbian oil company Nis-Gazprom Neft, said lube demand in the
region is bogged down in a weak economy. In addition, she said, local companies
find it difficult to compete against international brands. Kolb also discussed Nis-
Gazprom Nefts plan to build an API Group II and naphthenic base oil plant.
The boundaries of the Balkans are subject to interpretation. For the purpose of
her presentation, Kolb defined them as Romania, Bulgaria and Albania, plus the
seven nations that formerly made up Yugoslavia Slovenia, Croatia, Bosnia and
Herzegovina, Serbia, Macedonia, Montenegro and Kosovo. (Serbia still considers
Kosovo part of its territory, but more than 95 nations have recognized it as an
independent nation.)
Small Share of Europe is nothing to stir excitement.
Kolb, who is Nis-Gazprom Nefts director of After a weak recovery in 2011, the market
marketing and research and development, said slowed down last year, due to the Euro-zone
the Balkans is a sliver of Europes lubricant crisis. But we are optimists. This market will
market, accounting for just 3.5 percent of the rise and develop.
continents demand. She cited estimates by Three countries account for nearly three
Kline and Co. consultancy that Europe con- quarters of overall lube demand in the Bal-
sumed approximately 7 million metric tons of kans. By volume, Romania and Bulgaria are
lubes in 2012, compared to just 245,000 tons the regions biggest lubricant consumers, with
for the Balkans. annual consumption of 87,700 tons and 50,000
The Balkans share of the European market tons, respectively, followed by Serbia, with
should increase, since lubricant demand in the 37,500 tons. Next come Croatia (24,500 tons),
Balkans is increasing while in Europe it is fall- Bosnia and Herzegovina (18,400 tons) and Slo-
ing, but Kolb said the trend for the Balkans still venia (11,200 tons), then Albania (9,300 tons),
= 2,000 tons/year
SLOVENIA
C R O AT I A
ROMANIA
BOSNIA
AND
HERZEGOVINA SERBIA
BULGARIA
MONTENEGRO
MACEDONIA
ALBANIA
Planned Project*
Serbia Novi Sad Nis -Gazprom Neft 100,000 - 80,000
120,000
Macedonia 5,100 tons), Kosovo (4,200 tons) East will be [viewed] with great caution and
and Montenegro (2,200 tons). suspicion and are not very popular.
Kolb described the sub-regional market as Companies in the standard segment, she con-
crowded. It is a highly competitive market tinued, are trying to push low-grade, cheap
with nearly 70 lubricant producers, ranging lubes many of them not even branded.
from multinational oil companies to small Numerous small companies try to enter the
independent lube manufacturers. segment, but find it difficult to compete even
The Balkans lubricant market is segmented there.
into two categories: premium and regular. People in this region are oriented toward
Leaders in the premium segment are the premium brands or popular domestic com-
traditional brands of BP Castrol, Mobil, Total, panies, Kolb said. End users are afraid of
Shell, Selenia and Valvoline. In the regular buying fake oils, which were common in past
segment are the brands of two Russian oil ma- years. As a result, small, unknown companies
jors, Lukoil and Zarubezhneft [which owns Oil are hardly acceptable.
Refinery Modrica in Bosnia and Herzegovina Kolb confirmed that Nis-Gazprom Neft is
and operates in the region under the trademark not among the sub-regions leading suppliers,
Nestro], Hungarys MOL, Bulgarian producer but she claimed that the companys lubricant
Prista Oil, Polands PKN Orlen and the Croa- business is expanding, primarily in Serbia. The
tian company Optima Group, Kolb said. company markets lubes under the Nisotek
brand. Nis is experiencing very steep growth
Tough Competition on the local market and is becoming a key
Kolb acknowledged that companies in the lubricant brand, she said. The company has
latter group would like to gain footholds in already established distribution channels in the
the premium segment, but to date they have region. Besides its network of gas and service
generally not succeeded. The companies that stations in Serbia, Gazprom Neft has its own
control that part of the market are all from branches already up and running in Roma-
Western Europe or are large international nia, Bulgaria and Bosnia, we are also eyeing
companies, she said, noting that their brands the Greek market. The biggest volume of our
are well-known around the world. Large finished products will be offered through these
companies from Eastern Europe or the Middle Continued on page 28
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Continued from page 26 After a series of armed conflicts, including the
distribution channels and a smaller volume civil wars that accompanied the break-up of
will be offered through open international Yugoslavia and the Kosovo War, the economy
tenders. in the Balkans is less developed than anywhere
Nis-Gazprom Nefts competitor in Serbia in the European Union.
is Fam, an independent lubricants manufac- Like much of Europe, the sub-region has
turer from Krushevac, a town in central been slow to recover from the recession and its
Serbia. In this past decade, Fam has estab- subsequent economic crises. Largely because
lished a firm foothold in the sub-regional of this, lubricant demand is not expected to
lubricant market. return to pre-recession levels until 2016.
According to Kolb, most lubricant compa-
nies in the Balkans have done little to explore Base Oils from Serbia
export markets outside the sub-region. Nis- Base oil capacity in the Balkans and the rest
Gazprom Neft is making plans to do so, how- of Central Europe, has received few upgrades,
ever. In the future we expect more exports to but Nis-Gazprom Neft says it is pushing
Turkey and Africa, as well as Central, Eastern through with one despite the uninspiring lubes
and Southern Europe, she said. outlook. Gazprom has said it will invest 75
Like most places, lubricant demand in the million to build a base oil plant at the Novi Sad
Balkans depends mostly on economic activity refinery. Officials say the new plant will have
and demographics. That being the case, it does capacity to make 180,000 to 200,000 tons per
not look like the market should expect much year and will open by the second quarter of
help in the next few years. The population in 2015.
the sub-region, currently 52 million, is growing Around 100,000 to 120,000 t/y of that
at an average annual rate of just 0.28 percent. capacity will be for paraffinic Group II stocks,
and 20,000 t/y of lubricants. ing plant produced 30,000 tons, and and there is an increasing demand
the Moscow (Fryazino) plant produced there for both the companys premium
Gazproms Eye on Northern Europe more than 30,000 tons. Together, the finished products and for the base
Gazprom disclosed in March that two blending plants shipped 20,000 oils, Truhan said.
it plans to buy or build a lube blend- tons of finished lubricants to Finland Continued on page 32