11. December 2014   8:37 pm
Dr. K. L. Mittal, Dr. Robert H. Lacombe

Dr. K. L. Mittal, Dr. Robert H. Lacombe

  X-RAY PHOTOELECTRON SPECTROSCOPY – XPS

 In last months issue of the INVISIBLE UNIVERSE essay series we established two fundamental reasons why surfaces remain essentially invisible to us even though they are the most common entity with which we interact every waking moment.  The first reason was the fact that our eyes only detect about 2% of the radiation that any given surface can beam at us making us rely on special experimental technologies such as XPS in order to discern otherwise invisible surface structures.  The second reason is that surfaces are subject to the laws of quantum mechanics which determines not only the details of surface structure but also governs the interactions of all forms of radiation with the atomic and molecular entities of which all surfaces are composed.

 Last month’s discussion laid out the fundamental precepts of quantum theory and we now apply them to understand the workings of the XPS experiment.

 As pointed out in last months discussion the essence of the XPS experiment is when an X-Ray ( a high energy photon) impinges on a surface causing an electron ( called a photo electron due to being ejected by a photon) to be ejected from the surface.  The laws of quantum mechanics insure that the ejected electron will come off at a very specific energy which uniquely identifies the type of atom from which it was ejected.   This fact is what makes the XPS experiment so useful in probing the chemistry of any given surface.  To understand this better we need to understand a little more about how quantum mechanics determines the atomic and molecular structure of all matter.

 The story basically begins with a series of  experiments carried out by Hans Geiger and Ernst Marsden1 over the time period from 1908 to 1913 where they were bombarding gold foils with alpha particles and detecting how the particles were scattered.  Up to that time no one really had any idea as to what to expect.  The mechanics of materials at the time assumed all matter to be a sort of homogenous continuum and on the basis of that assumption the best guess was that the particles would pass straight through or be somehow absorbed by the material.  What they found instead was that a fraction of the particles were scattered through large angles up to 180 degrees. Ernst Rutherford the Director of the Cavendish Laboratory commented on these remarkable results as follows:

 It was quite the most incredible event that has ever happened to me in my life. It was almost as incredible as if you fired a 15-inch shell at a piece of tissue paper and it came back and hit you. On consideration, I realized that this scattering backward must be the result of a single collision, and when I made calculations I saw that it was impossible to get anything of that order of magnitude unless you took a system in which the greater part of the mass of the atom was concentrated in a minute nucleus. It was then that I had the idea of an atom with a minute massive centre, carrying a charge.

 This remarkable insight led to the notion that atomic matter was something like a miniature solar system where electrons orbit a central nucleus much as earth and the planets orbit the sun.  This all seemed quite plausible for a while since it was known that positive and negative particles attracted each other by an inverse square power law much as the sun attracts each of the planets.  This notion quickly fell apart, however, since the then well known laws of electrodynamics unambiguously predicted that such a system would be unstable.  Classical electrodynamics clearly predicted that the orbiting electrons would quickly radiate away their orbital energy and fall into the central nucleus.

 The conundrum of how atomic matter manages to exist was solved only when physicists attacked the problem using the principles of quantum theory.  In particular Schrödingers equation could be solved exactly for hydrogen, the simplest atom of all, and the resulting solution provided a remarkable template for working out the atomic structure of the rest of the periodic table and in fact provided the theoretical foundation of why the periodic table exists.  The picture that emerged is that a typical atom consists of a small ultra dense positively charged nucleus surrounded by a cloud of electrons where each electron occupies what is called a quantum eigenstate with a very sharply defined quantized energy level.

 At this point we have to wonder what on earth is a quantum eigenstate?  To proceed further we need to pass through the looking glass into the nether world of atomic matter as describe quantum theory which is the most consistent and accurate description that we have.  Ostensibly, from the work of Rutherford and his colleagues, the typical atom consists of negatively charged electrons somehow circulating around a positively charged center being held in a tightly contained cluster by the inverse square Coulomb interaction.  The first thing to note is that the notion that the electrons circle around the nucleus in a manner similar to the way the planets circle around the Sun is completely out the window.  The Heisenberg Uncertainty Principle in particular dictates that we cannot know, even in principle, where inside the atom a particular electron might be at any given time.  All we can know is where the electron tends to spend most of its time, i.e. the probability of finding the electron at any given point at any given time instant.  This comes about because quantum theory dictates that the state of any given electron is prescribed by what is known as a wave function which must be a solution of Schrödingers equation which leads us into the realm of some fairly abstract mathematics dealing with the solutions of differential equations.  Sorting through the details of solving Schrödingers equation would lead us rather far into the hinterlands of differential equation theory but we don’t have to make that journey to appreciate the final result.  The basic results that emerge from laboring through the details are as follows:

Lacombe1

Figure: Approximate energy level diagram for atomic matter

 1) The time independent solutions of Schrödingers equation which describe the atom at equilibrium are solutions to what is commonly known as an eigenvalue problem.

 2) The typical eigenvalue problem states that the differential equation under consideration can have solutions only if certain key parameters have very specific values which arise out of the general eigenvalue solution procedure.

 3) For the case of a simple atom such as hydrogen the key parameters are the spatial coordinates of the orbiting electron or what are commonly called its degrees of freedom.  In Cartesian coordinates these are the (x,y,z) position values.  For atoms it is more convenient to use spherical coordinates so instead of  (x,y,z) we use (ρ,θ,φ) i.e. a radial coordinate plus two angular coordinates.

 4) Thus, for the hydrogen atom the state of the electron is described by 3 eigenvalues one for each independent coordinate.  For the radial coordinate ρ the eigenvalue is called n where n can be any integer 1,2,3 …4. For the angular coordinate θ the quantum number is designated by the integer l which must be less than or equal to n – 1 or in symbols l # n – 1.  For the φ coordinate the eigenvalue number is designated by m which is subject to the constraint -l # m # +l

 5) There is yet one more phantom degree of freedom the electron can have and that is its spin which is designated by the symbol σ and can take on only the values ±1/2.  The electron spin is a wholly unexpected and mysterious degree of freedom that has to exist since it accounts for the magnetic moment of the electron.

 Figure: Approximate energy level diagram for atomic matter

6) The final piece of the puzzle which completes the quantum

description is the Pauli exclusion principle which simply states that no two electrons within an atom can have exactly the same quantum numbers.  Thus each electron must be described by different values of the numbers n,l,m and s.

 The above half dozen results that arise out of solving Schrödingers equation for the hydrogen atom form the basis of the energy level diagram depicted in figure (1).  Thus the energy of the electron which depends on all the degrees of freedom, but primarily on n, must also be quantized and therefore must be depicted by sharply defined discreet levels as shown in the figure.

 This is really a rather wondrous result as it lets us piece together atomic structure and the periodic table from the simple hydrogen atom up to very complex multi electron structures.  Lets cobble together the first few atoms to see how it works:

 1) HYDROGEN: With only one electron which occupies the lowest energy level traditionally designated by the label s which stands for angular momentum l=0.  The x axis labels in figure (1) correspond to the θ quantum number l and again by tradition is given the labels s, p, d, f … corresponding to the l values 0, 1, 2, 3, … respectively.  So for the hydrogen electron in its lowest energy state corresponding to n = 1 it can only have l = 0 according to rule 5 above and thus m must also be 0 according to the same rule.  The spin quantum number σ can be either ±1/2. Thus from the point of view of quantum theory the hydrogen electron is described by the following quadruplet of magic numbers (n,l,m,σ) = (1,0,0,1/2) where in the absence of any external magnetic field the spin quantum number σ could be either + or – ½.

 2) HELIUM: As the process continues to more complex atoms with more electrons we simply fill the levels shown in figure (1) one by one always filling the lowest energy levels first so that at equilibrium the atom has the lowest possible energy.  Helium has a nucleus with 2 protons and thus accommodates two electrons to achieve electrical neutrality and the lowest possible energy configuration has both electrons in the n = 1 quantum level with l = m = 0.  Now the Pauli exclusion principle comes into effect and dictates that one electron will have spin value +1/2 and the other -1/2.  By rule 6 above the n = 1 quantum level is now filled with one electron in the (1,0,0,+½) state and the other in the (1,0,0,-½) state.   Once an n level has the maximum number of electrons allowed by the above rules it is said to be filled and atoms with a filled n level tend to be very stable.  Thus helium is at a filled level and is predicted to be very stable as is well attested by experiment.

Lacombe2

Figure: XPS spectrum of a clean silicon wafer

 LITHIUM: Adding one more electron brings us to the element lithium with three electrons.  The first two electrons go into the n = 1 state with l = 0 and σ = ±1/2. Since the n = 1 state is now filled the third electron has no choice but to move into the n = 2 level with l = 0 and σ = ½ which is the 2s level shown in figure(1).

 HIGHER ATOMS: The process continues with the next element beryllium having 4 electrons completely filling the 1s and 2s levels.  The next atoms consisting of boron through neon must move into the next higher angular momentum state with l = 1 and designated as the 2p level in figure(1).  Since l = 1 now allows the m quantum number to take on the values -1, 0, +1 this level can hold up to 6 more electrons since each m level can accommodate 2 electrons by Pauli’s exclusion principle.  So the next 6

electrons go into the 2p level in the diagram and account for boron through neon.  At neon the 2p level is completely filled and neon is thus predicted to be a chemically stable molecule as is also born out in experiment.  The process continues progressively filling the higher energy levels shown in figure(1) and terminates finally at uranium with 92 electrons and thus 92 protons in the nucleus.  At this level of electric charge the electromagnetic forces in the nucleus reach a par with the normally much stronger nuclear forces and the nucleus itself becomes unstable and prone to fission.  Thus uranium is the largest atom found naturally in the environment though even larger atoms have been produced in large accelerators they have very short lifetimes.

 The above picture immediately implies that the electronic configurations of the different atoms provide unique tags for identifying each one since each configuration comes with a unique binding energy which is simply the energy required to remove an electron from a specific energy level into the void.  Consider for example a fluorine atom sitting on a surface.  The 1s electrons in fluorine have a binding energy of 17.4 ev (electron  volts) so if we see electrons at this energy being emitted from the surface we know that fluorine must be present. This is the basic concept underlying the XPS experiment.  The XPS spectrometer basically bombards the surface with X-rays which have sufficient energy to blast electrons bound to the various surface atoms out of their energy levels and then sorts the emitted electrons by their unique binding energies thus revealing which atoms are present at the surface.  Also the XPS experiment samples only the very top layers of the sample since once an electron has been emitted from its energy level it cannot travel very far through the surrounding material since its electric charge causes it to interact strongly with all the surrounding atoms which can capture or deflect it back into the substrate.  A free electron can typically go no more that about 100 angstroms through the material before being captured or deflected so in effect the electons which are ejected come from the top 100 angstroms of the surface effectively making XPS a surface sensitive technique. 

Figure(2) shows an XPS spectrum of a nominally clean silicon wafer which as manufactured consists of 100% pure single crystal silicon.  The XPS spectrometer, however, reveals a surprisingly different picture of the surface of the wafer.  Those in the microelectronics industry know that an initially clean silicon surface will react fairly rapidly with ambient oxygen to form a layer of silicon dioxide SiO2.  After a day or so sitting out in a clean room the initially pure silicon surface gathers a layer of SiO2 up to about 1000 angstrons thick which is way too thin to be detected by the human eye but is readily revealed in the XPS spectrum in figure(2).  The large central peak in the figure comes from electrons emitted from the oxygen 1s level in the SiO2.  The two small peaks to the far right come from the silicon 2s and 2p levels respectively.  This is not all, however, as the peak just to the right of the central oxygen 1s peak comes from the carbon 1s level and reveals that a contamination layer of a carbon containing molecule is also present.  This carbon contaminant most likely comes from some hydrocarbon or another which are present in nearly every ambient atmosphere.  Finally, the very tiny peak to the left of the central oxygen line reveals that a minute amount of fluorine is present as this peak represents electrons being emitted from the fluorine 1s level.  It is quite unusual for fluorine to be present on a clean silicon wafer and the contaminant level revealed in figure(2) entered through a rather surreptitious mechanism and also caused some rather unexpected problems with the adhesion behavior of this surface.

 Figure(2) represents a clear example of the invisible nature of surfaces by revealing three properties of a supposedly clean silicon wafer that would have been entirely invisible to the naked eye.

 1Geiger, Hans; Marsden, Ernest. “The Laws of Deflexion of α Particles through Large Angles”. Philosophical Magazine. Series 6 25 (148): 604-623(1913)

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27. May 2013   4:45 pm
Andy Stecher

Andy Stecher
Elgin, IL

The second installment in this series addresses the opposite of the first, creating a hydrophobic surface.  First we must ask what they are and why such a surface would be desired.  There are a number of answers but as a colleague of mine wisely says ‘Plasma is not a panacea’.

Hydrophobic surfaces are by-definition surfaces with lower energy states than the 72 mN/m (dyne) energy level at which water is attracted.  In essence, this is a surface water does not like to be on.  Droplets may form through condensation or be placed on them directly, but they will not spread.  They prefer their own level of energy and therefor contract to have the smallest contact with the surface they can muster.  This is what you see when water beads up on the freshly-waxed hood of your car.  The water may be held in place by gravity, but like a kid in the Principal’s office, they don’t want to be there.

So the first thing that comes to mind is that these coatings are designed to keep things dry.  That is the ‘How’, and here are some of the reasons why:  By repelling water on the edges of a case, you are keeping it away from damaging what is inside.  This same property can be used to divert small flows to the areas where you want them in micro-fluidic devices, such as medical test apparatus.  They will also resist water-based liquids such as paints or adhesives and minimize their ability to be permanently bonded to surfaces.  This makes a material easier to clean.

The coatings applied using our PlasmaPlus deposition system are based on the same SiOx chemistry used for hydrophilic coatings, with modifications to the process to make the surface energy as low as possible.  In most cases this is not below the as-molded surface energy of less expensive polymers such at polypropylene or HDPE, but it is much lower than the energy levels of most metals.  For this reason, the hydrophobic properties of these coatings are best used to inhibit corrosion.  They can resist the accumulation of physi-adsorbed water which can be a driver for corrosion.  Due to it’s other bonding characteristics, this same layer can act to promote adhesion in non-water-based systems.  The end result is a water-repellent bondline that is also chemically bonded by adhesive used.  This can be used to seal metal surfaces with much greater reliability than just cleaning and adhesive, thus extending part life dramatically!

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8. March 2013   5:10 pm
Andy Stecher

Andy Stecher
Elgin, IL

We get many inquiries regarding our coating technology.  Hydrophilic, hydrophobic, insulative, protection from the elements; you name it, there is someone out there that is looking for the tailored properties I’ve mentioned and more.  All mentioned are possible with our technology, however not in all scenarios and material combinations.  Is a series of blogs I will attempt to address the typical end goals of customers and where we can help the most.

Hydrophilicity is the most common request, and we can satisfy it via a few methods.  It is a measurement of how easily water wets out across a surface which is also a measurement of how functional (receptive to bonding) that surface is.  Our standard atmospheric plasma will typically elevate the surface energy of a material to a point well in excess of 72 dynes, which is where water wets out across a surface.  Similarly, we can deposit a glass-like nano-layer and elevate it’s surface energy to above 72 dynes as well.  The reason to use this coating rather than activate the material directly is that not all materials have strong longevity of treatment or are chemically receptive to all material combinations. Softer materials or those with many additives may only hold treatment for a few minutes before observing a drop. However if you properly adhere the coating to the surface while it is freshly activated the coating will be permanently adhered.  This layer can in turn be activated and will exhibit great longevity of treatment and can provide a necessary link between dissimilar materials.

The surfaces will only stay active/clean if you keep them that way.  A highly functional surface with oil smeared on it is now an oil surface. Additionally, that oil has likely rendered the plasma treatment neutral, requiring another cleaning and functionalization (whether by coating or just standard plasma). Luckily, with plasma there is little concern with treating a part again and you can regain the desired properties with ease.

By coating the work piece you have chosen the surface you want rather than having that be dictated by your material choice.  This opens up the design process as ‘design for assembly’ often means choosing materials that are easily bonded and now that can be almost any material with a PlasmaPlus coating!

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12. December 2012   1:47 am
Mikki Larner

Mikki Larner
Belmont, CA

The last few months have been a whirlwind of conferences, speaking engagements, trade shows, customer visits, lots of meetings, a few visits to our North American headquarters (Chi town), Canadian offices, the mother ship (Germany), and a sprinkling of board meetings.

One of the highlights was attending the Biointerface 2012 meeting in Dublin. http://www.surfaces.org/

(Oh, when in Dublin, I highly recommend dining at the Winding Stair for delicious tastes of fresh unadulterated seafood  http://winding-stair.com/.  MAKE A RESERVATION or be prepared with a warm coat as you walk around waiting for your 10 pm table.)

The folks at UCD and Surfaces.org pulled together an excellent forum with a tremendous focus on use of plasma for “medicine” and let us in to the labs at UCD for a tour to include a demonstration of our Openair tool. http://www.ucd.ie/surfaces/facilities.htm

I have pages and pages of notes from the meetings and want to share a few stand out quotes and notes relevant to our technology:

“Interface influences failures”

Mr. Reto Luginbuehl (RMS Foundation, Switzerland)
The impacts on interface include: biology, modulus, surface chemistry, wear, morphology, infection, roughness to name just a few. It is so important to remember this when designing a program. Everything needs to be tested…not just surface energy with water. Need to understand all types of interactions with the surface for a successful product design.

Dr. Anna Belu, Medtronic, had an excellent case study about contamination which hit close to home as plasma is often used to remove UNEXPECTED contamination from various sources such as packaging or residue from gloves.

There were excellent poster presentations. One standout was from UCD. They report superphobic (150deg+) surfaces via atmospheric plasma using siloxane precursors. Sounds like there are some stability issues with the surface, but nonetheless, the advances in AP are promising.

Professor Buddy Ratner provided the keynote on “Emerging Biointerface Solutions – Translating in vitro results to the In Vivo Environment” and provided one of the best quotes of the conference (I don’t recall who originally make the statement, so Prof. Ratner can take the cred.):

“Engineering is the instrument of civilization”

His talks are always interesting and he is a dynamic speaker.

Prof. David Grainger followed with his very passionate presentation on correlating in vitro and in vivo as well – specifically for anti microbial. His point about understating patient genetic profiles/genetic dispositions as part of the solution in reducing infection is the future. Clinical testing / device testing (pre market) is limited to a specific population thus doesn’t capture the true effectiveness of the device. Unfortunately setting up an in vitro test protocol to screen our diverse population is not feasible due to $$$. So his point, well taken, is if the FDA will allow products that are proven SAFE on the market, the efficacy data will build as the product as used.

Mr. Bob Ward, ExThera (former PTG now DSM), presented on controlling surface chemistry for treating bacteremia and sepsis. Of interest to me were his comments about how surface density is greatly affected by structure. An import variable in plasma process development programs is appreciating the structure and surface area of a device and result on surface chemistry.

Dr. Marcela Bilek, University of Sydney, presented on “Bioactivation of surfaces using embedded radicals.” Great talk on use of plasma for infusion (my interpretation) of reactive species into bulk of polymers. She notes metals as well, but sounds like she is creating an interface on top of the metal. An important point of her talk and others is that wet chemistries can be timely, toxic, slow and expensive — reinforcing the benefit of plasma as an alternative. In some examples, wet chemistry processes take upwards of 60 hours. This can often be reduced or replaced in full by a plasma process at 5 to 10 or 20 minutes.

Overall it was a thought provoking conference and a great opportunity to network with the surfaces community. I look forward to next year!

This will probably be my last entry for the year….off to Germany for our annual sales meeting and back home for some R&D, OOPS, I mean R&R.
Happy new year!

Collegue Graham Porcas

Openair Plasma in Dublin, Colleague Graham Porcas demonstrating the equipment

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5. December 2012   1:50 am
Khoren Sahagian

Khoren Sahagian

A proprietary PTS surface formulation is enabling SUPER omni-phobic surfaces on everything from machine tooling to porous media.  This novel surface chemistry maximizes water contact angles in a manner that appears to almost defy gravity (see photograph below).  The most impressive part of the process is that it is tunable to varying degrees of surface phobicity ranging from simple water, to oil, and finally even isopropyl alcohol!  Unlike dip coating methods that exhaust exotic monomers such as POSS (fluorodecyl polyhedral oligomeric silsesquioxane) the PTS vacuum plasma process uses almost no monomer and requires no thermal or UV curing steps.  This means true conformal coating of complex geometries with high yield and using a method that is superior in material and energy efficiency.

When deposited on machine molds and tooling the omni-phobic surface coating may act as a mold release, slip agent, & inhibit accumulation of debris.  Improved serviceability increases manufacturing efficiency by extending machine component lifetime and reducing the costs & frequency of scheduled maintenance programs.  Furthermore coating a thin film using plasma preserves micro-scale topography and ensures a permanent covalent bond with the substrate without the use of a primer or liquid etchant.  Because the omni-phobic film is derived from a plasma vapor phase it may even deposit into the tortuously small pore sizes of contemporary filtration media.  The coating is resistant to a wide range of temperature & chemistry.  Recent investigation of the surface treatment also demonstrates bacteriostatic characteristics which may possibly be exploited as an anti-microbial surface or to improve yield in cell transfer labware.

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Andy Stecher

Andy Stecher
President Plasmatreat USA
Elgin, IL

Editorial October 2012

Dear Reader:

Recently I visited the IMTS Show in Chicago’s McCormick Place, composed of its four very large exhibition halls. IMTS means International Machinery and Technolgy Show, North America’s largest machinery producer and supplier exhibition. Hosting exhibitors and visitors from 119 countries, IMTS 2012, which ran Sept. 10-15 at Chicago’s McCormick Place, covered 1.248 million net square feet of exhibit space with 1,909 exhibiting companies. Over 100,000 people attended the event. Very impressive indead. I remember this show from the early 2000’s when it had moved to the surburbs, Rosemont, IL, and it had trouble filling up a show area that was much smaller than McCormick Place. During my time at the show, a lot of people talked about “reshoring”, bringing production back to North America typically from Asia. The reasons for that seemed manifold but many of the concerns included increased supply chain costs, time for shipments, quality problems, communication difficulties based on language problems, concerns with Intellectual Property aspects, political uncertainties and many more.

Manufacturing in North America is experiencing a revival. Note this just 3 years ago, the Big Three automakers saw their factories running around 50 percent capacity. Now, it’s predicted they will be at greater than 100 percent capacity by year’s end. It’s uplifting news for the automotive industry, and manufacturing as a whole.

In a few days we are celebrating Manufacturing Day 2012 in the United States, another step to promote Manufacturing in our hemisphere: http://www.mfgday.com/event. It is a joyous occasion which will hopefully grow in popularity in the years to come. Check out a participating manufacturer near you and be impressed by modern manufacturing technology.

Still the problem we have in our country is that there is a lack of skilled workers. Since the 1970’s it has become the mantra that “only getting a college degree is the path to a successful career”. That is a failed plan. Less than 50% of freshman students graduate with a Bachelor degree, many of them incur large student debts which they have to pay back, degree or no degree. The latter of course excacerbates the individual situation. A failed college degree leaves the individual with a loss of time, a loss of money and little perspective where to go next in findng a decent paying job.

Learning a trade particularly in manufacturing is a great alternative. Yes, making things has a strong future. Creating value by making something will always be part of our society, part of what we do. Robots and automation have lowered costs and reduced mundane manual tasks in recent decades. That process will continue to increase productivity and lower operational costs. But skilled operators such as for CNC machining are currently in demand but will be in the years and decades ahead.

To compensate the shortfall that built up in prior decades there are many fledgling initiatives to address this problem. One example is the Center for Labor and Community Research in Chicago, IL (www.clcr.org). According to its Executive Director, Dan Swinney, the organization is working to rediscover, redefine and rebuild advanced manufacturing in the United States. Dan is pointng out that over 600,000 high-skill, high pay manufacturing jobs currently remain unfilled. There are pilot programs to alleviate this status. First CLCR initiated the Manufacturing Renaissance Council (MRC). MRC is a strategic, public/private partnership that operates regional programs in support of advanced manufacturing.  According to the MRC advanced manufacturing is the development and production of high-tech, complex products. An economy based on advanced manufacturing holds the greatest potential to create sustainable, long-term economic growth; rebuild the American middle class; and solve the global environmental crisis. CLCR, as one example, is working with Austin Polytechnical Academy (www.austinpolytech.org) to interest young students in learning industry-recognized machining credentials from NIMS (National Institute for Metalworking Skills). http://www.austinpolytech.org/apa-senior-torres-hughes-featured-huffington-post. Illinois based Elgin Community College is hosting their first Manufacturer’s Symposium on October 25 www.elgindevelopment.com/workforcedevelopment.  Furthermore according to the Daily Herald, the U.S. Department of Labor has awarded $12.9 million in federal funding to expand Harper College’s (HCC) new Advanced Manufacturing program to schools across Illinois (HCC, Palatine, IL) http://www.dailyherald.com/article/20120920/business/709209820/print/.

The Germany Embassy and its consulates around the country have initiated CEO roundtables and efforts to attract companies, especially German companies in the USA in this case, to help train a new generation of highly skilled workers. http://www.gaccsouth.com/en/news/single-view/artikel/ceo-roundtable-for-carolinas-discusses-skilled-workforce-development/?cHash=7db5b5d5b9638db9efba303c33d3ee0d. According to the Embassy website ‘through the “Skills Initiative,” the German Embassy is bringing together German and American businesses and local education/training providers with the aim of developing training programs best suited to businesses’ needs. The embassy launched “Skills Initiative” to identify and spread best practices in sustainable workforce development in the USA.

My company Plasmatreat North America (Elgin, IL, Ancaster, ON, Belmont, CA)  is a strong advocate of “Made in the USA”. Our state-of-the-art equipment keeps production competitive, lowers costs, increases employee safety and is finally very positive for the environment as harmful and costly chemicals are replaced. For example Plasma Plus, a new innovation, just won the German Engineering price at the 2012 Hannover Fair, the largest industrial trade show in the world. http://www.plasmatreat.com/news/72_industry-award-2012_hanover-fair.html

Call me to discuss how we can help make American manufacturing great again.

Till next time,

Andy

 

 

 

 

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6. August 2012   4:53 am
Mikki Larner

Mikki Larner
Belmont, CA

Low pressure plasma is a controlled method for modifying the surfaces of materials. Our core competency is in modifying polymers. We’ve modified almost every type of polymer from silicones to fluoropolymers. These products range in size from nano-powders to 5 foot wide webs and membranes. Our company has been modifying life science materials for over 30 years. These include drug delivery platforms, fluidic devices, assay tools, ophthalmic Devices, implantable engineering polymers, stents, leads and their delivery devices.

The most practiced technology is activation (or functionalization) for subsequent adhesion attachment. In a functionalization process, the plasma species energy is used to break surface layer molecular bonds and leads to an altered surface chemistry. The plasma chemistry (and the substrate) drives the resulting functional groups.

Our laboratory includes 100s of different chemistries derived from gases and vapors from liquids. We’ve conducted sublimation work as well. The technology routinely is used for introducing chemistries that traditionally are conducted via wet chemistry. The technology offers tremendous controls and a short process cycle (< 15 minutes).

For the life sciences, typical functionalizations include:
• Hydroxyl
• Carboxylic
• Carbonyl
• Amine
• Vinyl
• Glycidyl
• Thiol

These groups can be closely coupled to a surface or distanced by chains.

Customers request these groups for attachment to:

• Amino acids, peptide attachment
• Coatings to resist biofilm attachment, coagulation
• Antimicrobials
• Biomolecular immobilizations
• Polyethylene Glycol (PEG)
• Hyaluronic acid
• Polylactic acid or polylactide (PLA)
• Surfactant coatings
• Hydrogels

We also practice thin film depositions (all organic). This process is called Plasma Enhanced Chemical Vapor Deposition (PECVD).

Typical coatings are around 40 – 4000 Angstrom thick. These coatings are dry. Coatings include:

• Polystyrene, Polyethylene
• Fluoropolymer, fluoroacrylates
• Siloxane (also via Openair)
• PEGylated (Tetraglyme)
• Aminated
• Polyacrylate
• Hydroxyethyl methacrylate (HEMA)
• Ethylene Oxide

Customers request these coatings for:
• Interfaces (or tie layers)
• Hydrophobicity
• Oleophobicity
• Lubricity/decreased COF (dry)
• Biocompatibility
• Functionalization
• Chemical resistance
to name a few.

Primarily we modify devices and this does include combination devices. As polymers are being used more and more for target therapies, plasma has become a viable means for modifying surfaces to change release capabilities or modify other surface properties.

The technology is versatile. Controlled. Inexpensive. There is no waste. It is environmentally and workplace safe.

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Mikki Larner

Mikki Larner
Vice President Sales & Marketing
Belmont, CA

Editorial May 2012

Process Design Step 1:

Variables to consider when designing a surface modification program

 

I lied, partially.

I said that my next blog would be a trip report (sadly, Dyana said it was overcast) and power of plasma for modification of materials for the life sciences industry.   I’m not ready to jump into specific applications, rather want to start with some of the basics to a successful surface modification program.

I’ll start with Step 1.  Q&A.

The beginning of any lab development program typically involves a thorough Q&A session.   At the minimum, I want to know:

 

1.  Substrate

2.  Product environment

3.  Desired surface performance goal

 

The success, based on my experience, of a surface modification program relies on a thorough (if possible) understanding of these three items as 1 and 2 greatly impact 3.

For each question, there are 10s if not 100s of sub-questions that can shift outcome considerably.   I spoke about some of these recently at Hantel Technology  http://www.youtube.com/watch?v=gZemVc790oQ  and am summarizing a partial list of variables for each question below.

 

  1. SUBSTRATE.  Tell me about (I’m polymer focused):
    1. Resin selection/Metal properties
    2. Composite properties
    3. Manufacturing practice (molded, extruded, cast).  Are you starting with a machined part for R&D and then possibly considering molding for production.  We may talk about molecular weight distribution as well.
    4. Cure mechanism
    5. Cure temperatures
    6. Hardness (durometer)/crystallinity
    7. Topography
    8. Tacticity
    9. Additives (stabilizers, pigments, nucleating agents, plasticizers, etc)
    10. Propensity for migration of additives
    11. Propensity for molecular rotation
    12. Finishes
    13. Mold release materials
    14. Machining debris
    15. Moisture retain/absorption/adsorption
    16. Cleanliness (and how is the substrate cleaned prior to plasma)
    17. Manufacturing controls for said substrate
    18. Throughput targets

 

  1. ENVIRONMENT.  Once treated, please tell me about the next steps in processing and environment as these variables may impact surface performance and stability:
    1. See Item #1.9 above.  Bloom, migration of Internal impurities
    2. Adhesive technique (if bonding) and cure mechanism
    3. Potential for oxidation
    4. Chemical exposure
    5. Sterilization technique
    6. Subsequent assembly step (are you heat sealing?)
    7. Subsequent cleaning steps and techniques (are you IPA wiping part 100X times during assembly?)
    8. Handling (glove selection and practices)
    9. Storage (Packaging materials, Temperatures)

 

  1. SURFACE PROPERTIES.  What do you want as we have many variables to consider to provide the desired outcome.  Rather than listing the myriad of applications we practice, I’ll focus on variables that we consider in designing an experimental plan.

 

    1. Type of equipment (Corona, Atmospheric, Low Pressure)
    2. Steps and type of process (Cleaning, Etching, Activation, Functionalization, PECVD, Grafting, Crosslinking)
    3. Chemistry (gas, liquid vapor, sublimated solids, combinations).
    4.  Temperature of substrate, chamber, liquid/solid
    5. Pressure (flow driven, throttled, pumping capacity)
    6. Fixturing and fixture materials (does it contribute to dark space?)
    7. Power (continuous, pulsed, duty cycle, frequency)
    8. Time (3o seconds or 10 minutes)

BUT WAIT.  There is more!

VALIDATION TECHNIQUE/SURFACE ANALYSIS

Even the choice of how to validate the surface can impact the results.  Our chief technologist, Steve Kaplan, loves to say “don’t throw the baby out with the bathwater.”   It is not unusual for a customer to overlook the success of the process by improper selection of the validation method.    Test the product in the ultimate application.  Techniques used and considered at our laboratories include:

 

  • Surface energy testing
  • Dyne-cm, contact angle
  • fluid choice
  • Adhesion testing
  • Wear and abrasion testing
  • Friction testing
  • Hardness testing
  • Surface analysis
  • X-ray Photoelectron Spectroscopy (XPS)
  • Scanning Electron Microscopy (SEM)
  • AFM Atomic Force Microscopy
  • Fourier Transform Infrared Spectroscopy (FTIR)
  • Chemical resistance
  • Gas permeation / vapor barrier testing

 

This list isn’t to overwhelm.   I don’t expect answers to all of these questions nor do we screen every possible combination of variables.  We know where to start if you can provide us with the basics about  1 (Substrate), 2 (Environment of use) and 3 (Desired surface performance) so that we can design efficiently and effectively the best surface for your application.

Next blog…no promises.

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Andy Stecher

Andy Stecher
President Plasmatreat USA
Elgin, IL

Editorial April 2012

America and Canada are a truly great countries. Both regions are characterized by truly freedom loving people, both feature strong democracies despite the daily stalemates and political quabbles.  While their economies in general are powerful and have created some of the largest wealth per capita in the world, the recent 10-15 years have been marked by, in my view, myopic activities in industry: Manufacturing was given up on. With China achieving first “most favored nation status” and then later gaining access to the WTO, thus allowing for tax and duty favored imports, many manufacturing companies started to believe that they could not compete with China as well as other countries in the SE Asia region with their low wages and other low operating costs. Comprehensive new supply chain systems were set up, new operating and trading relationships were established, more and more company managers became ex-patriates. Some companies that wanted to continue producing product in North America were forced by large retailers such as WalMart to move their operations to a China location. The common crede became: Operating our production in China is the better way, there is no such future in North America.  

I disagreed from the Get-Go. I always believed that America needs manufacturing. One needs to build things to create value. Our countries cannot simply be service and consumption oriented societies. We saw what happened if when relied on the finance/banking sector alone. It created huge wealth only for a very few and when it all went wrong, we were all asked to pay the bill.

Manufacturing creates jobs at all levels, stimulates personal and professional creativity, helps shape products and processes and let us focus on the future by taking direct control. Plasmatreat works with manufacturers all over the world creating better and more productive operating environments. Here in Canada and the USA we have the potential to reclaim a top spot in the global arena of manufacturers. Designing and building product creates not only possibilities domestically but also sets the stage for successful exports. The USA in particular has been suffering from a negative trade deficit for several decades now. We need to think about reversing the flow of dollars into America not away from America. We need to support the Reindustrialization of America – we need to believe again in manufacturing. Plasmatreat together with our many industrial partners continuously are presenting ideas how to create competitive operating environments right here in North America. Our projects reach into various markets such as Solar, Medical, Packaging, Automotive and Electronics. We look foward to mastering the challenge to compete with low cost production countries, but we believe we can. Do you, too?

Till next time,

Andy

 

 

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